Fabric care compositions comprising cellulose binding domains

ABSTRACT

The present invention relates to fabric care compositions comprising one or more amino acid sequence(s) comprising a Cellulose Binding Domain for providing fabric care. In a further embodiment, the present invention relates to fabric care compositions wherein the amino acid sequence comprising one or more cellulose binding domains is linked to a softening protein.

FIELD OF THE INVENTION

The present invention relates to fabric care compositions comprising anamino acid sequence comprising a Cellulose Binding Domain (CBD).

BACKGROUND OF THE INVENTION

Modern laundry detergent and/or fabric care compositions contain variousdetergent ingredients having one or more purposes in obtaining fabricswhich are not only clean but also have retained appearance andintegrity. Therefore, detergent components such as perfumes, soilrelease agents, fabric brightening agents, fabric softeners, chelants,bleaching agents and catalysts, dye fixatives and enzymes, have beenincorporated in laundry detergent and/or fabric care compositions. Oneof such specific example is the use of enzymes, especially proteases,lipases, amylases and/or cellulases.

In particular, cellulase enzymes are used in detergent/fabric carecompositions for their cleaning and fabric care benefits. The activityof cellulase is one in which cellulosic fibres or substrates arehydrolised by the cellulase and is depending on the particular functionof the cellulase, which can be endo- or exo-cellulase, and on therespective hemicellulases. The cellulose structures are depolymerized orcleaved into smaller and thereby more soluble or dispersible fractions.This activity in particular on fabrics provides a cleaning,rejuvenating, softening and generally improved handfeel characteristicsto the fabric structure. It is known in the art through protein analysisthat cellobiohydrolases, major endoglucanases and bacterial cellulasesposses a bifunctional organisation in the form of a catalytical coredomain and a smaller cellulose binding domain separated by a linker orflexible hinge stretch of amino acids.

In recent years, consumer desirability for fabric conditioningcompositions has risen. Fabric softening compositions impart severaldesirable properties to treated garments including softness and staticcontrol. Fabric softness of laundered garments is typically achieved bydelivering a quaternary ammonium compound to the surface of the fabric.Consumer desirability for durable press fabric garments, particularlycotton fabric garments, has also risen. Durable press garments includethose garments which resist wrinkling of the fabric both during wear andduring the laundering process. Durable press garments can greatlydecrease the hand work associated with laundering by eliminating ironingsometimes necessary to prevent wrinkling of the garment. However, inmost commercially available durable press fabrics, the fabric's abilityto resist wrinkling is reduced over time as the garment is repeatedlyworn and laundered. Furthermore, coloured garments have a tendency towear and show appearance losses. A portion of this colour loss may beattributed to abrasion in the laundering process, particularly inautomatic washing machines and automatic laundry dryers. Moreover,tensile strength loss of fabric appears as an unavoidable result ofmechanical/chemical action due to use/wearing or washing.

As indicated above, there is a continuous need for a fabric carecomposition, which can provide fabric softness and provide, refurbish orrestore tensile strength, anti-wrinkle, anti-bobbling and anti-shrinkageproperties to fabrics, as well as provide static control, colourappearance and fabric anti-wear properties and benefits.

The above objective has been met by formulating fabric care compositionscomprising one or more amino acid sequence(s) comprising a CelluloseBinding Domain (CBD).

Enzymes linked to Cellulose Binding Domains are described in the art: WO91/10732 novel derivatives of cellulase enzymes combining a core regionderived from an endoglucanase producible by a strain of Bacillus spp.,NICMB 40250 with a CBD derived from another cellulase enzyme or acombining a core region derived from another cellulase enzyme with a CBDderived from said endoglucanase, for improved binding properties.WO94/07998 describes cellulase variants of a cellulase classified infamily 45, comprising a CBD, a Catalytically Active Domain (CAD) and aregion linking the CBD to the CAD, wherein one or more amino acidresidues have been added, deleted or substituted and/or another CBD isadded at the opposite end of the CAD. WO95/16782 relates to the cloningand high level expression of novel truncated cellulase proteins orderivatives thereof in Trichoderma longibrachiatum comprising differentcore regions with several CBDs. WO97101629 describes cellulolytic enzymepreparation wherein the mobility of the cellulase component may bereduced by adsorption to an insoluble or soluble carrier e.g. via theexisting or newly introduced CBD. WO97/28243 describes a process forremoval or bleaching or soiling or stains from cellulosic fabricswherein the fabric is contacted in aqueous medium with a modified enzymewhich comprises a catalytically active amino acid sequence of anon-cellulolytic enzyme selected from amylases, proteases, lipases,pectinases and oxidoreductases, linked to an amino acid sequencecomprising a cellulose binding domain and a detergent compositioncomprising such modified enzyme and a surfactant.

However, none of these documents disclose fabric care compositionscomprising one or more amino acid sequence(s) comprising one or moreCellulose Binding Domain, for fabric care benefits.

SUMMARY OF THE INVENTION

The present invention relates to fabric care compositions comprising oneor more amino acid sequence(s) comprising one or more cellulose bindingdomain, providing fabric care.

In a further embodiment, the present invention relates to fabric carecompositions wherein the amino acid sequence comprising a cellulosebinding domain, is linked to a softening protein.

The fabric care compositions of the present invention can furthercomprise a softening ingredient selected from cationic surfactants, atransferase enzyme and/or clays.

DETAILED DESCRIPTION OF THE INVENTION

An essential element of the fabric care compositions of the presentinvention is an amino acid sequence comprising a cellulose bindingdomain. This amino acid sequence comprising a cellulose binding domain(CBD) can be a naturally occurring sequence or can be modified :encompassed are cross-linked CBDs, i.e. amino acid sequences comprisinga cellulose binding domain which are cross-linked to each other and/orCBDs further linked to a softening protein, i.e. an amino acid sequencecomprising a cellulose binding domain linked to a softening protein.

Indeed, the present invention encompasses several embodiments:

In a first embodiment, the present invention relates to a fabric carecomposition comprising one or more amino acid sequence(s) comprising acellulose binding domain. It has been surprisingly found that suchcompositions comprising one or more CBDs, provide softening, abrasionresistance and pilling prevention. Indeed, without wishing to be boundby theory, it is believed that the CBDs adsorb on the fibres of thefabric. Such adsorbed CBDs protect the fabric's fibers and therebyprevent the fibrillation of the cellulosic fibres. Moreover, CBDs areproteins and therefore provide softening.

In a second embodiment, the present invention encompasses a fabric carecomposition comprising cross-linked amino acid sequences comprising acellulose binding domain. It has been surprisingly found that suchcross-linked CBDs provide softness, prevent the fibrillation ofcellulosic fibers as indicated above and also restore tensile strength,prevent the apparition of wrinkles, and increase the hydrophilicity ofsynthetic fibers. Indeed, without wishing to be bound by theory, it isbelieved that each cross-linked CBD can adsorb at opposite sites of thedamaged fibers and thereby can restore tensile strength. Moreover,

In a third embodiment, the present invention relates to a fabric carecomposition comprising the above describe embodiments which are furtherlinked to a softening protein. Without wishing to be bound by theory, itis believed that the addition of a cellulose binding domain to asoftening protein, allows a higher concentration of the softeningprotein onto the fabric, i.e. a closer and/or more lasting contact,resulting in a more efficient activity. Such modified softening proteinshave an increased affinity (relative to unmodified softening protein)for binding to a cellulosic fabric or textile.

The above described fabric care composition may further comprise asoftening ingredient selected from cationic surfactants, a transferaseenzyme and/or clays.

Cellulose Binding Domain (CBD)

In the present context, the terms “amino acid sequence comprising a CBDor Cellulose Binding Domain or CBD” are intended to indicate an aminoacid sequence capable of effecting binding of the cellulase to acellulosic substrate (e.g. as described in P. Kraulis et al.,Determination of the three-dimensional structure of the C terminaldomain of cellobiohydrolase I from Trichoderma reesei. A study usingnuclear magnetic resonance and hybrid distance geometry-dynamicallysimulated annealing. Biochemistry 28:7241-7257, 1989). Theclassification and properties of cellulose binding domains are presentedin P. Tomme et al., in the symposium “Enzymatic degradation of insolublepolysaccharides” (ACS Symposium Series 618, edited by J. N. Saddler andM. H. Penner, ACS, 1995).

Cellulose-binding (and other carbohydrate-binding) domains arepolypeptide amino acid sequences which occur as integral parts of largepolypeptides or proteins consisting of two or more polypeptide aminoacid sequence regions, especially in hydrolytic enzymes (hydrolases)which typically comprise a catalytic domain containing the active sitefor substrate hydrolysis and a carbohydrate-binding domain for bindingto the carbohydrate substrate in question. Such enzymes can comprisemore than one catalytic domain and one, two or threecarbohydrate-binding domains, and they may further comprise one or morepolypeptide amino acid sequence regions linking the carbohydrate-bindingdomain(s) with the catalytic domain(s), a region of the latter typeusually being denoted a “linker”.

Examples of hydrolytic enzymes comprising a cellulose-binding domain arecellulase, xylanases, mannanases, arabinofuranosidases, acetylesterasesand chitinases. “Cellulose-binding domains” have also been found inalgae, e.g. in the red alga porphyra purpurea in the form of anon-hydrolytic polysaccharide-binding protein [see P. Tomme et al.,Cellulose-binding domains—Classification and Properties in EnzymaticDegradation of Insoluble Carbohydrates, John N. Saddler and Michael H.Penner (Eds.), ACS Symposium Series, No. 618 (1996)]. However, most ofthe known CBDs (which are classified and referred to by P. Tomme et al.(op. cit.) as “cellulose-binding domains”] derive from cellulases andxylanases.

In the present context, the term “cellulose-binding domain” is intendedto be understood in the same manner as in the latter reference (P. Tommeet al., op. cit.) The P. Tomme et al. reference classifies more than 120“cellulose-binding domains” into 10 families (I-X) which may havedifferent functions or roles in connection with the mechanism ofsubstrate binding. However, it is to be anticipated that new familyrepresentatives and additional families will appear in the future.

In proteins/polypeptides in which CBDs occur (e.g. enzymes, typicallyhydrolytic enzymes such as cellulases), a CBD may be located at the N orC terminus or at an internal position.

The part of a polypeptide or protein (e.g. hydrolytic enzyme) whichconstitutes a CBD per se typically consists of more than about 30 andless than about 250 amino acid residues. For example, those CBDs listedand classified in Family I in accordance with P. Tomme et al. (op. cit.)consist of 33-37 amino acid residues, those listed and classified inFamily IIa consist of 95-108 amino acid residues, those listed andclassified in Family VI consist of 85-92 amino acid residues, whilst oneCBD (derived from a cellulase from Clostridium thermocellum) listed andclassified in Family VII consists of 240 amino acid residues.Accordingly, the molecular weight of an amino acid sequence constitutinga CBD per se will typically be in the range of from about 4 kD to about40 kD, and usually below about 35 kD.

Cellulose binding domains can be produced by recombinant techniques asdescribed in H. St{dot over (a)}lbrand et al., Applied and EnvironmentalMicrobiology, Mar. 1995, pp. 1090-1097; E. Brun et al., (1995) Eur. J.Biochem. 231, pp. 142-148; J. B. Coutinho et al., (1992) MolecularMicrobiology 6(9), pp. 1243-1252

In order to isolate a cellulose binding domain of, e.g. a cellulase,several genetic engineering approaches may be used. One method usesrestriction enzyme to remove a portion of the gene and then to fuse theremaining gene-vector fragment in frame to obtain a mutated gene thatencodes a protein truncated for a particular gene fragment. Anothermethod involves the use of exonucleases such as Ba131to systematicallydelete nucleotides either externally from the 5′ and the 3′ ends of theDNA or internally from a restricted gap within the gene. Thesegene-deletion methods result in a mutated gene encoding a shortened genemolecule whose expression product may then be evaluated forsubstrate-binding (e.g. cellulose-binding) ability. Appropriatesubstrates for evaluating the binding ability include cellulosicmaterials such as Avicel™ and cotton fibres. Other methods include theuse of a selective or specific protease capable of cleaving a CBD, e.g.a terminal CBD, from the remainder of the polypeptide chain of theprotein in question.

Once a nucleotide sequence encoding the substrate-binding(carbohydrate-binding) region has been identified, either as cDNA orchromosomal DNA, it may then be manipulated in a variety of ways to fuseit to a DNA sequence encoding the amino acid sequence of interest. TheDNA fragment encoding the carbohydrate-binding amino acid sequence, andthe DNA encoding the amino acid sequence of interest are then ligatedwith or without a linker. The resulting ligated DNA may then bemanipulated in a variety of ways to achieve expression. Preferredmicrobial expression hosts include certain Aspergillus species (e.g. A.niger or A. oryzae), Bacillus species, and organisms such as Escherichiacoli or Saccharomyces cerevisiae.

Preferred CBDs for the purpose of the present invention are selectedfrom the group consisting of: CBDs CBHII from Trichoderma reesei, CBDsCenC, CenA and Cex from Cellulomonas fimi, CBD CBHI from Trichodermareesei, CBD Cellulozome from Clostridium cellulovorans, CBD E3 fromThermonospora fusca, CBD-dimer from Clostridium stecorarium (NCIMB11754)XynA, CBD from Bacillus agaradherens (NCIMB40482) and/or CBD family 45from Humicola insolens. More preferred CBD for the purpose of thepresent invention are the CBD CenC from Cellulomonas fimi, CBDCellulozome from Clostridium cellulovorans and/or the CBD originatingfrom the fungal Humicola Insolens cellulase sold under the tradename“Carezyme” by Novo Nordisk A/S. Carezyme is an endoglucanase from family45, derived from Humicola insolens DSM1800, having a molecular weight ofabout 43 kDa and exhibiting cellulolytic activity

The fabric care composition can comprise one or more of the abovedescribed CBDs, any of these CBDs which are cross linked and/or furtherlinked to a softening protein and/or mixtures thereof. The cross-linkedCBDs of the present invention can comprise the amino acid sequencecomprising from 2 to 50, preferably 2 to 10 cellulose binding domains.The CBDs comprised in the fabric care compositions of the presentinvention may originate from different sources. The CBDs, thecross-linked CBDs and/or the CBD linked to a softening protein aregenerally comprised in the fabric care compositions of the presentinvention at a level of from 0.01% to 10% and preferably from 0.1% to 6%and in a concentrated fabric care composition, from 0.2% to 30%, from 2%to 20% by weight.

For example, as described by M. Linder et al in The Journal ofBiological Chemistry, Vol. 271, No. 35, Issue of August, pp 21268-21272,1996, a double CBD by fusing the N-terminal CBD of T. reesei CBHII tothe C-terminal CBD of CBHI by a linker region of 24 amino acids can beconstructed. The linker region contains three amino acid residues fromthe natural CBHII linker followed by 21 amino acid residues from thenatural CBHI linker. The double CBD was cloned an produced inEscherichia coli. It has been observed that the two domains interactduring binding on cellulose, resulting in a higher binding affinity ofthe double CBD than either of the two single domains by themselves.Construction of the Double CBD Peptide—All DNA manipulations wereperformed using standard protocols. The gene constructions were firstassembled into the vector pSP73 (Promega). The coding region for thepelB signal sequence of Erwinia carotovora was fused in frame with thecoding region of the first 41 N-terminal residues of CBHII derived fromthe plasmid pTTc9, which in turn was linked to the coding region of thelast 57 residues of CBHI derived from the plasmid pTTcl). For expressionin E. coli, the construction was inserted into the expression vectorpKK223-3, containing the isopropyl-β-D-thiogalactopyranoside-inducibletac promoter. The nucleotide sequence of the final construct wasverified by sequencing.

Fermentation—The E. coli cultivations for producing the double CBD werecarried out in a Chemap CMF laboratory fermenter with a working volumeof 1.5 liters. A pH of 7 was maintained throughout the fermentation, andthe rate of agitation was controlled to maintain constant dissolvedoxygen levels. During the exponential growth phase (15-20 h afterinoculation), isopropyl-β-D-thiogalactopyranoside was added to a finalconcentration of 0.5 mM to induce gene expression. The fermentation wascontinued until maximal levels of product had been reached (20-30 h).

Purification of the Double CBD—Culture supernatant was centrifuged(10.000 rpm, 45 min) and mixed with an equal volume of 20 mM phosphatebuffer, pH 8.0, containing 1.5 M ammonium sulfate and kept at 4° C.overnight. Precipitation was removed by centrifugation as above, and thesupernatant was filtered through a 0.45 μm Durapore (Millipore Corp.)membrane. The clarified supernatant was then loaded onto abutyl-Sepharose 4B column (Pharmacia Biotech Inc.) previouslyequilibrated with 10 mM phosphate buffer, pH 8.0, containing 0.75 Mammonium sulfate. The column was then washed with equilibration buffer,and the bound protein was eluted with 10 mM phosphate buffer, pH 8.0.The eluted peak fractions were loaded onto a Source RPC column(Pharmacia) equilibrated with Milli-Q water:trifluoroacetic acid(1000:1). Bound peptide was eluted with an increasing linear gradient ofacetonitrile:trifluoroacetic acid (1000:1). The purified peptide wasthen lyophilized. During all purification steps the double CBD wasidentified by the monoclonal antibody CI-89, which is specific towardthe CBHI CBD. All chromatographic steps were run on a fast proteinliquid chromatography (Pharmacia) system.

Proteolytic Cleavage—The lyophilized peptide was redissolved in 100 mMTris buffer, pH 8.2 (2 mg/ml) and 10 units of immobilized trypsin (SigmaT-4019) added per mg of peptide. The suspension was incubated at 37° C.overnight, purified by the chromatography on Source RPC media (seeabove), and then lyophilized. The cleavage products were characterizedand identified by amino acid analysis and MALDI-MS.

Analytical Techniques for the CBD Peptides—Purity control andquantification of CBD peptides was performed by RP-HPLC. A Pro-PepVydacC18 analytical column was used with gradient elution withwater:trifluoroacetic acid (1000:1) to acetonitrile:trifluoroacetic acid(1000:1). Absorbance at 225 nm was used for detection. Quantification ofpeptide in the culture supernatant was also possible by this technique.

Production and Purification of the Double CBD—The amino acid sequence ofthe processed form of the double CBD is shown in FIG. 1 (M. Linder et alin The Journal of Biological Chemistry, Vol. 271, No. 35, Issue ofAugust, pp 21268-21272, 1996). In fermentor cultivations of the E. coliWCM105 strain 60-80 mg/liter of the peptide was secreted into theculture medium, yielding 40-50 mg/liter of pure peptide (see FIG. 2—M.Linder et al in The Journal of Biological Chemistry, Vol. 271, No. 35,Issue of August, pp 21268-21272, 1996). The identity and correctprocessing of the peptide was verified by amino acid compositionanalysis. The peptide identity was also confirmed by Western blottingwith a monoclonal antibody specific for the CBHI CBD.

The fabric care composition can also comprise the above described aminoacid sequences further linked to a softening protein.

It has been found that enzyme proteins surprisingly show highadsorbability to a cellulosic fiber (EP 687 729). Enzyme proteins usedin the present invention are those generically defined as a class ofproteins having a particular structure for catalytic action. In otherwords, all proteins that possess a structure for catalytic action can beused, whether or not they exhibit catalytic action. However, enzymeproteins suitable for the purpose of the present invention are inactive.Inactivation can occur for example by inhibition, by the distortion ofthe three-dimensional structure for example by thermal or chemicalmeans. When proteins other than enzyme proteins are used, the effects ofthe present invention may be obtained to some extent, but sufficienteffect may not be achieved. Enzyme proteins have different biologicalorigins: animal, plant and microbial origins. Enzyme proteins of anyorigin are usable for the present invention.

Such enzyme proteins, as classified on the basis of enzyme reactiontype, include hydrolases, lyases, oxidoreductases, ligases, transferasesand isomerases, all of which are usable for the present invention. Apreference is given to hydrolases, exemplified by proteases (peptidase),glucosidases such as cellulase and amylase, and esterases such aslipase. The molecular weight of the enzyme protein is preferably notlower than 10,000, more preferably in the range of from 20,000 to300,000. Being not lower than 10,000 in molecular weight, some enzymeproteins cannot penetrate the single fiber/monofilament (lamellastructure) of cellulosic fibers such as a natural cellulose fiber andrayon. Also, they may not penetrate the monofilament of syntheticfibers, because the monofilament internal structure is dense. Enzymeadsorption sites of cellulosic fibers and synthetic fibers are thereforelimited to the surface of the single fiber/monofilament.

Preferably the softening enzyme protein will be chosen from inactiveenzyme comprising a CBD in nature, such as cellulase, xylanases,mannanases, arabinofuranosidases, acetylesterases and chitinases.

JP01280079 describes another type of softening proteins that can be usedin the fabric care compositions of the present invention. Thesesoftening proteins are polyamino acid resin solution that adhere tosynthetic, semi synthetic or cotton fabrics and thereby providesoftness. These polyamino acids are preferably alpha amino acid such asglutamic acid, glycine, ornithine, mono- or co-polymer such aspoly-gamma-L-glutamate.

Also suitable for the present invention are the C18 alkyl quaternarywheat protein derivatives sold under the tradename Coltide HQS by CrodaColloids Ltd. These wheat proteins derivatives generally included atlevels of 0.04% to 0.2% by weight, are known to. provide greatconditioning effect, i.e. to provide great handfeeling, softeness, toprevent fibres erosion of cotton and wool fabrics and to increase thelubricity of wool fibres.

Such amino acid sequence comprising one ore more CBDs and/or beingfurther linked to a softening proteins (referred to as CBD hybridsand/or softening protein hybrids) can be prepared and purified bymethods known in the art [see, e.g., WO 90/00609, WO 94/24158 and WO95/16782, as well as Greenwood et al., Biotechnology and Bioengineering44 (1994) pp. 1295-1305]. The production of enzymes hybrid is given inWO 91/10732 wherein novel derivatives of cellulase enzymes combining acore region derived from a Bacillus NICB 40250 endoglucanase with a CBDderived from another cellulase enzyme or a combining a core regionderived from another cellulase enzyme with a CBD derived from a BacillusNICB 40250 endoglucanase, are constructed. WO 95/16782 describes thecombinations of different core regions with several CBD and the cloningand high level expression of these novel truncated cellulase proteins orderivatives thereof, in Trichoderma longibrachiatum.

The CBD hybrid and/or softening protein hybrid may, e.g., be prepared bytransforming into a host cell a DNA construct comprising at least afragment of DNA encoding the cellulose-binding domain ligated, with orwithout a linker, to a DNA sequence encoding the other cellulose bindingdomain and/or softening protein of interest, and growing the transformedhost cell to express the fused gene. One relevant, but non-limiting,type of recombinant product (CBD hybrid and/or softening protein hybrid)obtainable in this matter—often referred to in the art as a “fusionprotein”—may be described by one of the following general formulae:A-CBD-MR-X-BA-X-MR-CBD-B

In the latter formulae, CBD is an amino acid sequence comprising atleast the cellulose-binding domain (CBD) per se.

MR (the middle region; a linking region) may be a bond, or a linkinggroup comprising from 1 to about 100 amino acid residues, in particularof from 2 to 40 amino acid residues, e.g. from 2 to 15 amino acidresidues. MR may, in principle, alternatively be a non-amino-acid linker(See below). X is an amino acid sequence comprising another cellulosebinding domain and/or an amino acid sequence comprising theabove-mentioned, inactive sequence of amino acid residues of apolypeptide encoded by a DNA sequence encoding the softening protein ofinterest.

The moieties A and B are independently optional. When present, a moietyA or B constitutes a terminal extension of a CBD or X moiety, andnormally comprises one or more amino acid residues.

It will thus, inter alia, be apparent from the above that a CBD in asoftening protein hybrid of the type in question may be positionedC-terminally, N-terminally or internally in the softening proteinhybrid. Correspondingly, an X moiety in a softening protein hybrid ofthe type in question may be positioned N-terminally, C-terminally, orinternally in the softening protein hybrid.

Softening protein hybrids of interest in the context of the inventioninclude softening protein hybrids which comprise more than one CBD, e.g.such that two or more CBDs are linked directly to each other, or areseparated from one another by means of spacer or linker sequences(consisting typically of a sequence of amino acid residues ofappropriate length). Two CBDs in an softening protein hybrid of the typein question may, for example, also be separated from one another bymeans of an -MR-X- moiety as defined above. One or more cellulosebinding domain can be linked to the N-terminal and/or C-terminal partsof the cellulase core region. Any part of a CBD can be selected,modified, truncated etc.

Preferably, attention will be paid in the construction of CBD hybridand/or softening protein hybrids of the type in question to thestability towards proteolytic degradation. Two- and multi-domainproteins are particularly susceptible towards proteolytic cleavage oflinker regions connecting the domains. Proteases causing such cleavagemay, for example, be subtilisins, which are known to often exhibit broadsubstrate specificities [see, e.g.: Grøn et al., Biochemistry 31 (1992),pp. 6011-6018; Teplyakov et al., Protein Engineering 5 (1992), pp.413420]. Glycosylation of linker residues in eukaryotes is one Nature'sways of preventing proteolytic degradation. Another is to employ aminoacids which are less favoured by the surrounding proteases. The lengthof the linker also plays a role in relation to accessibility byproteases. Which “solution” is optimal depends on the environment inwhich the softening protein hybrid is to function. When constructing newCBD hybrid and/or softening protein hybrid molecules, attention will bepreferably paid to the linker stability.

Plasmids

Preparation of plasmids capable of expressing fusion proteins having theamino acid sequences derived from fragments of more than one polypeptideis well-known in the art (see, for example, WO 90/00609 and WO95/16782). The expression cassette may be included within a replicationsystem for episomal maintenance in an appropriate cellular host or maybe provided without a replication system, where it may become integratedinto the host genome. The DNA may be introduced into the host inaccordance with known techniques such as transformation, microinjectionor the like.

Once the fused gene has been introduced into the appropriate host, thehost may be grown to express the fused gene. Normally it is desirableadditionally to add a signal sequence which provides for secretion ofthe fused gene. Typical examples of useful genes are:

-   1) Signal sequence—(pro-peptide)—carbohydrate-binding    domain—linker—CBD and/or softening protein sequence of interest, or-   2) Signal sequence—(pro-peptide)—CBD and/or softening protein    sequence of interest—linker—carbohydrate-binding domain,    in which the pro-peptide sequence normally contains 5-100, e.g.    5-25, amino acid residues. The recombinant product may be    glycosylated or non-glycosylated.    Linking Region

The term “linker” or “linking region” or “Middle region—MR” is intendedto indicate a region that might adjoin the CBD and connect it to anotherCBD or to the amino acid sequence of a softening protein. When present,this linking can be achieved chemically or by recombinant techniques.

An example of the recombinant technique describing the expression of anenzyme with the CBD of different origin is described in S. Karita etal., (1996) Journal of Fermentation and Bioengineering, Vol. 81, No. 6,pp. 553-556. Preferred linking regions are amino acid linking regions(peptides), some examples thereof are described in N. R. Gilkes et al.,Microbiol. Rev. 55, 1991, pp. 303-315. The linking region can comprisefrom 1 to about 100 amino acid residues, in particular of from 2 to 40amino acid residues, e.g. from 2 to 15 amino acid residues. As statedabove, it is preferred to use amino acids which are less favoured by thesurrounding proteases. Suitable amino acid linking regions are theHumicola insolens family 45 cellulase linker, the NifA gene ofKlebsiella pneumoniae-CiP linker, the E. coli OmpA gene-CiP linker, theE3 cellulase Thermomonospora fusca linker and the CenA cellulase linker;preferably the Humicola insolens family 45 cellulase linker and the E3cellulase Thermomonospora fusca linker.

Non amino acid/proteinic compounds, referred to as “non-amino acid” canalso be used for the linking of the catalytically active amino acidsequence to the CBD:

-   1) Suitable non-amino acid linking regions are the polyethylene    glycol derivatives described in the Shearwater polymers, Inc.    catalog of January 1996, such as the nucleophilic PEGs, the carboxyl    PEGs, the electrophilically activated PEGs, the sulfhydryl-selective    PEGs, the heterofunctional PEGs, the biotin PEGs, the vinyl    derivatives, the PEG silanes and the PEG phospholipids. In    particular, suitable non-amino acid linking regions are the    heterofunctional PEG, (X-PEG-Y) polymers from Shearwater such as    PEG(NPC)2, PEG-(NH2)2, t-BOC-NH-PEG-NH2, t-BOC-NH-PEG-CO2NHS,    OH-PEG-N H-tBOC, FMOC-NH-PEG-CO2NHS or PEG(NPC)₂ MW 3400 from Sigma,    glutaric dialdehyde 50 wt % solution in water from Aldrich,    disuccinimidyl suberate (DSS) form Sigma, γ-maleimidobutric acid    N-hydroxysuccinimide ester (GMBS) from Sigma,    1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC)    from Sigma and dimethyl suberimidate hydrochloride (DMS) from Sigma.-   2) Other suitable non-amino acid linking regions are    1-ethyl-3-(3-dimethylaminopropyl) carbodiimide,    N-ethyl-5-phenylisoaxolium-3-sulphonate,    1-cyclohexyl-3(2morpholinoethyl) carbodide metho-p-toluene    sulphonate, N-ethoxycarbonyl-2-ethoxy 1,2, dihydroquinoline or    glutaraldehyde.-   3) Also suitable are the crosslinkers described in the 1999/2000    Pierce Products Catalogue from the Pierce Company, under the heading    “Cross linking reagents the SMPH, SMCC, LC-SMCC compounds, and    preferably the Sulfo-KMUS compound.    Preferred chemical linking regions are PEG(NPC)2, (NH2)2-PEG,    t-BOC-NH-PEG-NH2, MAL-PEG-NHS, VS-PEG-NHS polymers from Shearwater    and/or the Sulfo-KMUS compound from Pierce.    Fabric Care and Detergent Components

Preferably, the fabric care compositions of the invention will containat least one additional. fabric care component. The precise nature ofthese additional components, and levels of incorporation thereof willdepend on the physical form of the composition, and the nature of thecleaning operation for which it is to be used.

The composition may comprise optional ingredients such as a dye fixingagent, a fabric softener compound and further optional ingredients. Thefabric care compositions of the present invention preferably furthercomprise a fabric care ingredient selected from cationic surfactants, atransferase enzyme and/or clays.

The composition of the invention can be employed in stand alone productincluding pre-or post-wash additives. It can also be employed It canalso be used in fully-formulated compositions including laundrycompositions as well as rinse added fabric softener compositions anddryer added compositions (e.g. sheets) which provide softening and/orantistatic benefits, and rinse added compositions.

Cationic Softeners

The fabric care compositions of the present invention preferably furthercomprise a cationic surfactant. It has been surprisingly found that thefabric care compositions of the present invention further comprising acationic surfactant, can provide improved fabric softness and provide,refurbish or restore enhanced tensile strength, anti-wrinkle,anti-bobbling and anti-shrinkage properties to fabrics, as well asprovide improved static control, color appearance and fabric anti-wearproperties and benefits.

Typical of the cationic softening components are the quaternary ammoniumcompounds or amine precursors thereof as defined hereinafter.

Quaternary Ammonium Fabric Softening Active Compound

(1) Preferred quaternary ammonium fabric softening active compound havethe formula

or the formula:

wherein Q is a functional unit having the formula:

each R unit is independently hydrogen, C₁-C₆ alkyl, C₁-C₆ hydroxyalkyl,and mixtures thereof, preferably methyl or hydroxy alkyl; each R¹ unitis independently linear or branched C₁₁-C₂₂ alkyl, linear or branchedC₁₁-C₂₂ alkenyl, and mixtures thereof, R² is hydrogen, C₁-C₄ alkyl,C₁-C₄ hydroxyalkyl, and mixtures thereof; X is an anion which iscompatible with fabric softener actives and adjunct ingredients; theindex m is from 1 to 4, preferably 2; the index n is from 1 to 4,preferably 2.

An example of a preferred fabric softener active is a mixture ofquaternized amines having the formula:

wherein R is preferably methyl; R¹ is a linear or branched alkyl oralkenyl chain comprising at least 11 atoms, preferably at least 15atoms. In the above fabric softener example, the unit —R¹ represents afatty alkyl or alkenyl unit which is typically derived from atriglyceride source. The triglyceride source is preferably derived fromtallow, partially hydrogenated tallow, lard, partially hydrogenatedlard, vegetable oils and/or partially hydrogenated vegetable oils, suchas, canola oil, safflower oil, peanut oil, sunflower oil, corn oil,soybean oil, tall oil, rice bran oil, etc. and mixtures of these oils.

The preferred fabric softening actives of the present invention are theDiester and/or Diamide Quaternary Ammonium (DEQA) compounds, thediesters and diamides having the formula:

wherein R, R¹, X, and n are the same as defined herein above forformulas (1) and (2), and Q has the formula:

These preferred fabric softening actives are formed from the reaction ofan amine with a fatty acyl unit to form an amine intermediate having theformula:

wherein R is preferably methyl, Q and R¹ are as defined herein before;followed by quaternization to the final softener active.

Non-limiting examples of preferred amines which are used to form theDEQA fabric softening actives according to the present invention includemethyl bis(2-hydroxyethyl)amine having the formula:

methyl bis(2-hydroxypropyl)amine having the formula:

methyl (3-aminopropyl) (2-hydroxyethyl)amine having the formula:

methyl bis(2-aminoethyl)amine having the formula:

triethanol amine having the formula:

di(2-aminoethyl) ethanolamine having the formula:

The counterion, X⁽⁻⁾ above, can be any softener-compatible anion,preferably the anion of a strong acid, for example, chloride, bromide,methylsulfate, ethylsulfate, sulfate, nitrate and the like, morepreferably chloride or methyl sulfate. The anion can also, but lesspreferably, carry a double charge in which case X⁽⁻⁾ represents half agroup.

Tallow and canola oil are convenient and inexpensive sources of fattyacyl units which are suitable for use in the present invention as R¹units. The following are non-limiting examples of quaternary ammoniumcompounds suitable for use in the compositions of the present invention.The term “tallowyl” as used herein below indicates the R¹ unit isderived from a tallow triglyceride source and is a mixture of fattyalkyl or alkenyl units. Likewise, the use of the term canolyl refers toa mixture of fatty alkyl or alkenyl units derived from canola oil.

In the following table are described non-limiting examples of suitablefabric softener according to the above formula. In this list, the term“oxy” defines a

unit, whereas the term “oxo” defines a -O- unit.Table IIFabric Softener Actives

-   N,N-di(tallowyl-oxy-2-oxo-ethyl)-N-methyl, N-(2-hydroxyethyl)    ammonium chloride;-   N,N-di(canolyl-oxy-2-oxo-ethyl)-N-methyl, N-(2-hydroxyethyl)    ammonium chloride;-   N,N-di(tallowyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;-   N,N-di(canolyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride-   N,N,N-tri(tallowyl-oxy-2-oxo-ethyl)-N-methyl ammonium chloride;-   N,N,N-tri(canolyl-oxy-2-oxo-ethyl)-N-methyl ammonium chloride;-   N-(tallowyloxy-2-oxo-ethyl)-N-(tallowyl)-N,N-dimethyl ammonium    chloride;-   N-(canolyloxy-2-oxo-ethyl)-N-(canolyl)-N,N-dimethyl ammonium    chloride;-   1,2-di(tallowyloxy-oxo)-3-N,N,N-trimethylammoniopropane chloride;    and-   1,2-di(canolyloxy-oxo)-3-N,N,N-trimethylammoniopropane chloride;    and mixtures of the above actives.

Other examples of quaternay ammoniun softening compounds aremethylbis(tallowamidoethyl)(2-hydroxyethyl)ammonium methylsulfate andmethylbis(hydrogenated tallowamidoethyl)(2-hydroxyethyl)ammoniummethyl-sulfate; these materials are available from Witco ChemicalCompany under the trade names Varisoft® 222 and Varisoft® 110,respectively.

Particularly preferred is N,N-di(tallowyl-oxy-2-oxo-ethyl)-N-methyl,N-(2-hydroxyethyl) ammonium chloride, where the tallow chains are atleast partially unsaturated.

Transferase Enzyme

The fabric care compositions of the present invention preferably furthercomprise a transferase enzyme. It has been surprisingly found that thefabric care compositions of the present invention further comprising atransferase enzyme, can provide improved fabric softness and provide,refurbish or restore enhanced tensile strength, anti-wrinkle,anti-bobbling and anti-shrinkage properties to fabrics, as well asprovide improved static control, color appearance and fabric anti-wearproperties and benefits

Transferase enzymes catalyse the transfer of functional compounds to arange of substrates. Particularly, the transferase of the invention havethe potential to transfer a chemical moiety, for example a methyl groupor a glycosyl group, from a small substrate to form oligomeric moleculesor elongate polymeric compounds. Using small substrates, the enzymeimproves the properties of garments by binding functional groups likemethyl, hydroxymethyl, formyl, carboxyl, aldehyde, ketone, acyl, aminoand phosphorous functional groups and/or transferring glycosyl residuesto the garment surface.

Without wishing to be bound by theory, it is believed that aminoacyltransferase of the IUPAC Classification EC 2.3.2 links the amino acid(s)of the CBDs, Cross-linked CBDs, the amino acid linking regions and/orthe softening proteins to the cotton fibres of the fabric and therebyprovide, refurbish or restore tensile strength. Moreover, it is believedthat glycosyl transferase of the IUPAC Classification EC 2.4 transferand link covalently the glycosyl carbohydrates that can be found on theCBDs, Cross-linked CBDs, the amino acid linking regions and/or thesoftening proteins to the fabric and thereby provide, refurbish orrestore tensile strength.

The aminoacyl transferases (EC 2.3.2) are enzymes transferring aminogroups from a donor, generally an amino acid, to an acceptor. Even morepreferred is the protein-glutamine γ-glutamyltransferase (EC 2.3.2.13),also available under the name transglutaminase.

The general properties of the glycosyltransferases is to transfer asugar from oligosaccharides to another carbohydrate as acceptor. Bothhexosyltransferases and pentosyltransferases can be used in theinvention.

Examples of suitable glycosyltransferases are galactosyl transferasesand fructosyltransferases, such as 1,4-β-galactosyltransferase;1,3-α-fructosyltransferase; 2,3-sialyl transferase; cyclodextringlycosyltransferase; N-acetylgluco- or -galactosaminyltransferase. Ofparticular interest is EC 2.4.1.24 1,4-α-D-glucan :1,4-a-D-glucan(D-glucose) 6-α-D-glucosyl transferase. A particulatemember of this enzyme is commercially available under the nameTransglucosidase L-500.

In addition to the glycosyltransferases discussed above, it has beenfound that mutant glycosyltransferases and/or glycosidase, examples ofwhich are described in PCT Application Publication No. WO 97/21822 to S.G. Withers Protein Eng. Net. Canada, improve the tensile strength andappearance of fabrics, e.g., reduce fabric wrinkles, enhance shaperetention and reduce shrinkage

Yet another enzyme that is of particular interest is cyclomaltodextringlucanotransferase (“CGT-ase”) (EC 2.4.1.19), which is commerciallyavailable from Amano and Novo Nordisk A/S.

Yet still another group of enzymes that is of particular interest isglucansucrases, of which dextransucrase (EC 2.4.1.5), aglycosyltransferase, is one example. Other glucansucrases that aresuitable for use in the compositions described herein include, but arenot limited to, various dextransucrases, alternansucrase andlevansucrase. Levansucrase is commercially available from Genencor.

These transferases are preferably incorporated into the fabric carecompositions in accordance with the invention at a level of from 0.0001%to 10%, more preferably from 0.0005% to 5%, most preferred from 0.001%to 1% pure enzyme by weight of the total composition.

The above-mentioned enzymes may be of any suitable origin, such asvegetable, animal, bacterial, fungal and yeast origin. Origin canfurther be mesophilic or extremophilic (psychrophilic, psychrotrophic,thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.).Purified or non-purified forms of these enzymes may be used. Nowadays,it is common practice to modify wild-type enzymes via protein/geneticengineering techniques in order to optimise their performance efficiencyin the fabric care compositions of the invention. For example, thevariants may be designed such that the compatibility of the enzyme tocommonly encountered ingredients of such compositions is increased.Alternatively, the variant may be designed such that the optimal pH,bleach and/or chelant stability, catalytic activity and the like, of theenzyme variant is tailored to suit the particular fabric conditioningand/or cleaning application.

In particular, attention should be focused on amino acids sensitive tooxidation in the case of bleach stability and on surface charges for thesurfactant compatibility. The isoelectric point of such enzymes may bemodified by the substitution of some charged amino acids, e.g. anincrease in isoelectric point may help to improve compatibility withanionic surfactants. The stability of the enzymes may be furtherenhanced by the creation of e.g. additional salt bridges and enforcingcalcium binding sites to increase chelant stability.

Color Care and Fabric Care Benefits

Technologies which provide a type of color care benefit can also beincluded. Examples of these technologies are metallo catalysts for colormaintenance. Such metallo catalysts are described in copending EuropeanPatent Application No. 92870181.2. Dye fixing agents, polyolefindispersion for anti-wrinkles and improved water absorbancy, perfume andamino-functional polymer (PCT/US97/16546) for colour care treatment andperfume substantivity are further examples of color care/fabric caretechnologies and are described in the co-pending Patent Application No.96870140.9, filed Nov. 7, 1996.

Fabric softening agents can also be incorporated into fabric carecompositions in accordance with the present invention. These agents maybe inorganic or organic in type. Inorganic softening agents areexemplified by the smectite clays disclosed in GB-A-1 400 898 and inU.S. Pat. No. 5,019,292. Organic fabric softening agents include thewater insoluble tertiary amines as disclosed in GB-A1 514 276 and EP-B0011 340 and their combination with mono C1214 C14 quaternary ammoniumsalts are disclosed in EP-B-0 026 527 and EP-B-0 026 528 anddi-long-chain amides as disclosed in EP-B-0 242 919. Other usefulorganic ingredients of fabric softening systems include high molecularweight polyethylene oxide materials as disclosed in EP-A-0 299 575 and 0313 146.

Preferably, the fabric care compositions of the present invention willcomprise a clay. It has been surprisingly found that the fabric carecompositions of the present invention further comprising a clay, canprovide improved fabric softness and provide, refurbish or restoreenhanced tensile strength, anti-wrinkle, anti-bobbling andanti-shrinkage properties to fabrics, as well as provide improved staticcontrol, color appearance and fabric anti-wear properties and benefits.

Levels of smectite clay are normally in the range from 2% to 20%, morepreferably from 5% to 15% by weight. Organic fabric softening agentssuch as the water-insoluble tertiary amines or dilong chain amidematerials are incorporated at levels of from 0.5% to 5% by weight,normally from 1% to 3% by weight whilst the high molecular weightpolyethylene oxide materials and the water soluble cationic materialsare added at levels of from 0.1% to 2%, normally from 0.15% to 1.5% byweight.

Dye Fixing Agent

The composition of the invention may optionally comprise a dye fixingagent. Dye fixing agents, or “fixatives”, are well-known, commerciallyavailable materials which are designed to improve the appearance of dyedfabrics by minimizing the loss of dye from fabrics due to washing. Notincluded within this definition are components which are fabricsofteners or those described hereinbefore as amino-functional polymers.

Many dye fixing agents are cationic, and are based on variousquaternized or otherwise cationically charged organic nitrogencompounds. Cationic fixatives are available under various trade namesfrom several suppliers. Representative examples include: CROSCOLOR PMF(July 1981, Code No. 7894) and CROSCOLOR NOFF (January 1988, Code No.8544) from Crosfield; INDOSOL E-50 (Feb. 27, 1984, Ref. No. 6008.35.84;polyethyleneamine-based) from Sandoz; SANDOFIX TPS, which is alsoavailable from Sandoz and is a preferred polycationic fixative for useherein and SANDOFIX SWE (cationic resinous compound), REWIN SRF, REWINSRF-O and REWIN DWR from CHT-Beitlich GMBH, Tinofix® ECO, Tinofix® FRDand Solfin® available from Ciba-Geigy.

Other cationic dye fixing agents are described in “Aftertreatments forimproving the fastness of dyes on textile fibres” by Christopher C. Cook(REV. PROG. COLORATION Vol. 12, 1982). Dye fixing agents suitable foruse in the present invention are ammonium compounds such as fattyacid—diamine condensates e.g. the hydrochloride, acetate, metosulphateand benzyl hydrochloride of oleyldiethyl aminoethylamide,oleylmethyl-diethylenediaminemethosulphate, monostearyl-ethylenediaminotrimethyl-ammonium methosulphate and oxidized products oftertiary amines; derivatives of polymeric alkyldiamines,polyamine-cyanuric chloride condensates and aminated glyceroldichlorohydrins.

A typical amount of the dye fixing agent to be employed in thecomposition of the invention is preferably up 90% by weight, preferablyup to 50% by weight, more preferably from 0.001% to 10% by weight, mostpreferably from 0.5% to 5% active by weight of the composition.

Fabric Softening Compound

Typical levels of incorporation of the softening compound in the fabriccare composition are of from 1% to 80% by weight, preferably from 5% to75%, more preferably from 15% to 70%, and even more preferably from 19%to 65%, by weight of the composition.

The fabric softener compound is preferably selected from a cationic,nonionic, amphoteric or anionic fabric softening component. Typical ofthe cationic softening components are the quaternary ammonium compoundsor amine precursors thereof as defined hereinafter.

Quaternary Ammonium Fabric Softening Active Compound

As described above, the fabric care compositions of the presentinvention preferably further comprise a cationic surfacants.

Amine Fabric Softening Active Compound

Suitable amine fabric softening compounds for use herein, which may bein amine form or cationic form are selected from:

-   -   (i)- Reaction products of higher fatty acids with a polyamine        selected from the group consisting of        hydroxyalkylalkylenediamines and dialkylenetriamines and        mixtures thereof. These reaction products are mixtures of        several compounds in view of the multi-functional structure of        the polyamines.

The preferred Component (i) is a nitrogenous compound selected from thegroup consisting of the reaction product mixtures or some selectedcomponents of the mixtures.

One preferred component (i) is a compound selected from the groupconsisting of substituted imidazoline compounds having the formula:

wherein R⁷ is an acyclic aliphatic C₁₅-C₂₁ hydrocarbon group and R⁸ is adivalent C₁-C₃ alkylene group.

Component (i) materials are commercially available as: Mazamide® 6, soldby Mazer Chemicals, or Ceranine® HC, sold by Sandoz Colors & Chemicals;stearic hydroxyethyl imidazoline sold under the trade names of Alkazine®ST by Alkaril Chemicals, Inc., or Schercozoline® S by Scher Chemicals,Inc.; N,N″-ditallowalkoyldiethylenetriamine;1-tallowamidoethyl-2-tallowimidazoline (wherein in the precedingstructure R¹ is an aliphatic C₁₅-C₁₇ hydrocarbon group and R⁸ is adivalent ethylene group).

Certain of the Components (i) can also be first dispersed in a Bronstedacid dispersing aid having a pKa value of not greater than about 4;provided that the pH of the final composition is not greater than about6. Some preferred dispersing aids are hydrochloric acid, phosphoricacid, or methylsulfonic acid.

Both N,N″-ditallowalkoyldiethylenetriamine and1-tallow(amidoethyl)-2-tallowimidazoline are reaction products of tallowfatty acids and diethylenetriamine, and are precursors of the cationicfabric softening agent methyl-1-tallowamidoethyl-2-tallowimidazoliniummethylsulfate (see “Cationic Surface Active Agents as Fabric Softeners,”R. R. Egan, Journal of the American Oil Chemicals'Society, January 1978,pages 118-121). N,N″-ditallow alkoyldiethylenetriamine and1-tallowamidoethyl-2-tallowimidazoline can be obtained from WitcoChemical Company as experimental chemicals.Methyl-1-tallowamidoethyl-2-tallowimidazolinium methylsulfate is sold byWitco Chemical Company under the tradename Varisoft® 475.

-   -   (ii)-softener having the formula:        wherein each R² is a C₁₋₆ alkylene group, preferably an ethylene        group; and G is an oxygen atom or an —NR— group; and each R, R¹,        R² and R⁵ have the definitions given above and A⁻ has the        definitions given above for X⁻.

An example of Compound (ii) is 1-oleylamidoethyl-2-oleylimidazoliniumchloride wherein R¹ is an acyclic aliphatic C₁₅-C₁₇ hydrocarbon group,R² is an ethylene group, G is a NH group, R⁵ is a methyl group and A⁻ isa chloride anion.

-   -   (iii)-softener having the formula:        wherein R, R¹, R², and A⁻ are defined as above.

An example of Compound (iii) is the compound having the formula:

wherein R¹ is derived from oleic acid.

Additional fabric softening agents useful herein are described in U.S.Pat. No. 4,661,269, issued Apr. 28, 1987, in the names of Toan Trinh,Errol H. Wahl, Donald M. Swartley, and Ronald L. Hemingway; U.S. Pat.No. 4,439,335, Burns, issued Mar. 27, 1984; and in U.S. Pat. No.3,861,870, Edwards and Diehl; U.S. Pat. No. 4,308,151, Cambre; U.S. Pat.No. 3,886,075, Bernardino; U.S. Pat. No. 4,233,164, Davis; U.S. Pat. No.4,401,578, Verbruggen; U.S. Pat. No. 3,974,076, Wiersema and Rieke; U.S.Pat. No. 4,237,016, Rudkin, Clint, and Young; and European PatentApplication publication No. 472,178, by Yamamura et al., all of saiddocuments being incorporated herein by reference.

Of course, the term “softening active” can also encompass mixedsoftening active agents. Preferred among the classes of softenercompounds disclosed herein before are the diester or diamido quaternaryammonium fabric softening active compound (DEQA).

Fully formulated fabric care compositions may contain, in addition tothe hereinbefore described components, one or more of the following.ingredients.

Liquid Carrier

Another optional, but preferred, ingredient is a liquid carrier. Theliquid carrier employed in the instant compositions is preferably atleast primarily water due to its low cost, relative availability,safety, and environmental compatibility. The level of water in theliquid carrier is preferably at least about 50%, most preferably atleast about 60%, by weight of the carrier. Mixtures of water and lowmolecular weight, e.g., <about 200, organic solvent, e.g., loweralcohols such as ethanol, propanol, isopropanol or butanol are useful asthe carrier liquid. Low molecular weight alcohols include monohydric,dihydric (glycol, etc.) trihydric (glycerol, etc.), and higherpolyhydric (polyols) alcohols.

Additional Solvents

The compositions of the present invention may comprise one or moresolvents which provide increased ease of formulation. These ease offormulation solvents are all disclosed in WO 97/03169. This isparticularly the case when formulating liquid, clear fabric softeningcompositions. When employed, the ease of formulation solvent systempreferably comprises less than about 40%, preferably from about 10% toabout 35%, more preferably from about 12% to about 25%, and even morepreferably from about 14% to about 20%, by weight of the composition.The ease of formulation solvent is selected to minimize solvent odorimpact in the composition and to provide a low viscosity to the finalcomposition. For example, isopropyl alcohol is not very effective andhas a strong odor. n-Propyl alcohol is more effective, but also has adistinct odor. Several butyl alcohols also have odors but can be usedfor effective clarity/stability, especially when used as part of a easeof formulation solvent system to minimize their odor. The alcohols arealso selected for optimum low temperature stability, that is they areable to form compositions that are liquid with acceptable lowviscosities and translucent, preferably clear, down to about 40° F.(about 4.4° C.) and are able to recover after storage down to about 20°F. (about minus 6.7° C.).

The suitability of any ease of formulation solvent for the formulationof the liquid, concentrated, preferably clear, fabric softenercompositions herein with the requisite stability is surprisinglyselective. Suitable solvents can be selected based upon theiroctanol/water partition coefficient (P) as defined in WO 97/03169.

The ease of formulation solvents herein are selected from those having aClogP of from about 0.15 to about 0.64, preferably from about 0.25 toabout 0.62, and more preferably from about 0.40 to about 0.60, said easeof formulation solvent preferably being at least somewhat asymmetric,and preferably having a melting, or solidification, point that allows itto be liquid at, or near room temperature. Solvents that have a lowmolecular weight and are biodegradable are also desirable for somepurposes. The more assymetric solvents appear to be very desirable,whereas the highly symmetrical solvents such as 1,7-heptanediol, or1,4-bis(hydroxymethyl) cyclohexane, which have a center of symmetry,appear to be unable to provide the essential clear compositions whenused alone, even though their ClogP values fall in the preferred range.The most preferred ease of formulation solvents can be identified by theappearance of the softener vesicles, as observed via cryogenic electronmicroscopy of the compositions that have been diluted to theconcentration used in the rinse. These dilute compositions appear tohave dispersions of fabric softener that exhibit a more unilamellarappearance than conventional fabric softener compositions. The closer touni-lamellar the appearance, the better the compositions seem toperform. These compositions provide surprisingly good fabric softeningas compared to similar compositions prepared in the conventional waywith the same fabric softener active.

Operable ease of formulation solvents are disclosed and listed belowwhich have ClogP values which fall within the requisite range. Theseinclude monools, C6 diols, C7 diols, octanediol isomers, butanediolderivatives, trinethylpentanediol isomers, ethyl methylpentanediolisomers, propyl pentanediol isomers, dimethylhexanediol isomers,ethylhexanediol isomers, methylheptanediol isomers, octanediol isomers,nonanediol isomers, alkyl glyceryl ethers, di(hydroxy alkyl) ethers, andaryl glyceryl ethers, aromatic glyceryl ethers, alicyclic diols andderivatives, C₃C₇ diol alkoxylated derivatives, aromatic diols, andunsaturated diols. Particularly preferred ease of formulation solventsinclude hexanediols such as 1,2-Hexanediol and 2-Ethyl-1,3-hexanedioland pentanediols such as 2,2,4-Trimethyl-1,3-pentanediol.

Dispersibility Aids

Relatively concentrated compositions containing both saturated andunsaturated diester quaternary ammonium compounds can be prepared thatare stable without the addition of concentration aids. However, thecompositions of the present invention may require organic and/orinorganic concentration aids to go to even higher concentrations and/orto meet higher stability standards depending on the other ingredients.These concentration aids which typically can be viscosity modifiers maybe needed, or preferred, for ensuring stability under extreme conditionswhen particular softener active levels are used. The surfactantconcentration aids are typically selected from the group consisting of(1) single long chain alkyl cationic surfactants; (2) nonionicsurfactants; (3) amine oxides; (4) fatty acids; and (5) mixturesthereof. These aids are described in WO 94/20597, specifically on page14, line 12 to page 20, line 12, which is herein incorporated byreference.

When said dispersibility aids are present, the total level is from 2% to25%, preferably from 3% to 17%, more preferably from 4% to 15%, and evenmore preferably from 5% to 13% by weight of the composition. Thesematerials can either be added as part of the active softener rawmaterial, (I), e.g., the monolong chain alkyl cationic surfactant and/orthe fatty acid which are reactants used to form the biodegradable fabricsoftener active as discussed hereinbefore, or added as a separatecomponent. The total level of dispersibility aid includes any amountthat may be present as part of component (1).

Inorganic viscosity/dispersibility control agents which can also actlike or augment the effect of the surfactant concentration aids, includewater-soluble, ionizable salts which can also optionally be incorporatedinto the compositions of the present invention. A wide variety ofionizable salts can be used. Examples of suitable salts are the halidesof the Group IA and IIA metals of the Periodic Table of the Elements,e.g., calcium chloride, magnesium chloride, sodium chloride, potassiumbromide, and lithium chloride. The ionizable salts are particularlyuseful during the process of mixing the ingredients to make thecompositions herein, and later to obtain the desired viscosity. Theamount of ionizable salts used depends on the amount of activeingredients used in the compositions and can be adjusted according tothe desires of the formulator. Typical levels of salts used to controlthe composition viscosity are from about 20 to about 20,000 parts permillion (ppm), preferably from about 20 to about 11,000 ppm, by weightof the composition.

Alkylene polyammonium salts can be incorporated into the composition togive viscosity control in addition to or in place of the water-soluble,ionizable salts above. In addition, these agents can act as scavengers,forming ion pairs with anionic detergent carried over from the mainwash, in the rinse, and on the fabrics, and may improve softnessperformance. These agents may stabilize the viscosity over a broaderrange of temperature, especially at low temperatures, compared to theinorganic electrolytes.

Specific examples of alkylene polyammonium salts include I-lysinemonohydrochloride and 1,5-diammonium 2-methyl pentane dihydrochloride.

Stabilizers

Stabilizers can be present in the compositions of the present invention.The term “stabilizer,” as used herein, includes antioxidants andreductive agents. These agents are present at a level of from 0% toabout 2%, preferably from about 0.01% to about 0.2%, more preferablyfrom about 0.035% to about 0.1% for antioxidants, and more preferablyfrom about 0.01% to about 0.2% for reductive agents. These assure goododor stability under long term storage conditions for the compositionsand compounds stored in molten form. The use of antioxidants andreductive agent stabilizers is especially critical for low scentproducts (low perfume).

Examples of antioxidants that can be added to the compositions of thisinvention include a mixture of ascorbic acid, ascorbic palmitate, propylgallate, available from Eastman Chemical Products, Inc., under the tradenames Tenox® PG and Tenox S-1; a mixture of BHT (butylatedhydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate, andcitric acid, available from Eastman Chemical Products, Inc., under thetrade name Tenox-6; butylated hydroxytoluene, available from UOP ProcessDivision under the trade name Sustane® BHT; tertiary butylhydroquinone,Eastman Chemical Products, Inc., as Tenox TBHQ; natural tocopherols,Eastman Chemical Products, Inc., as Tenox GT-1IGT-2; and butylatedhydroxyanisole, Eastman Chemical Products, Inc., as BHA; long chainesters (C₈-C₂₂) of gallic acid, e.g., dodecyl gallate; Irganox® 1010;Irganox® 1035; Irganox® B 1171; Irganox® 1425; Irganox® 3114; Irganox®3125; and mixtures thereof; preferably Irganox® 3125, Irganox® 1425,Irganox ® 3114, and mixtures thereof; more preferably Irganoxe 3125alone. The chemical names and CAS numbers for some of the abovestabilizers are listed in Table II below.

TABLE II Chemical Name used in Code of Antioxidant CAS No. FederalRegulations Irganox ® 1010 6683-19-8Tetrakis(methylene(3,5-di-tert-butyl- 4-hydroxyhydrocinnamate))methaneIrganox ® 1035 41484-35-9 Thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate) Irganox ® 1098 23128-74-7 N,N′-Hexamethylenebis(3,5-di-tert- butyl-4-hydroxyhydrocinnamamide) Irganox ® B 117131570-04-4 23128-74-7 1:1 Blend of Irganox ® 1098 and Irgafos ® 168Irganox ® 1425 65140-91-2 Calcium bis(monoethyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate) Irganox ® 3114 65140-91-2 Calciumbis(monoethyl(3,5-di-tert- butyl-4-hydroxybenzyl)phosphonate) Irganox ®3125 34137-09-2 3,5-Di-tert-butyl-4-hydroxy- hydrocinnamic acid triesterwith 1,3,5-tris(2-hydroxyethyl)-S- triazine-2,4,6-(1H, 3H, 5H)-trioneIrgafos ® 168 31570-04-4 Tris(2,4-di-tert-butyl-phenyl)- phosphiteExamples of reductive agents include sodium borohydride, hypophosphorousacid, Irgafos® 168, and mixtures thereof.Soil Release Agent

Soil Release agents are desirably used in fabric care compositions ofthe instant invention. Any polymeric soil release agent known to thoseskilled in the art can optionally be employed in the compositions ofthis invention. Polymeric soil release agents are characterized byhaving both hydrophilic segments, to hydrophilize the surface ofhydrophobic fibers, such as polyester and nylon, and hydrophobicsegments, to deposit upon hydrophobic fibers and remain adhered theretothrough completion of washing and rinsing cycles and, thus, serve as ananchor for the hydrophilic segments. This can enable stains occurringsubsequent to treatment with the soil release agent to be more easilycleaned in later washing procedures.

If utilized, soil release agents will generally comprise from about0.01% to about 10.0%, by weight, of the fabric care compositions herein,typically from about 0.1% to about 5%, preferably from about 0.2% toabout 3.0%.

The following, all included herein by reference, describe soil releasepolymers suitable for use in the present invention. U.S. Pat. No.3,959,230 Hays, issued May 25, 1976; U.S. Pat. No. 3,893,929 Basadur,issued Jul. 8, 1975; U.S. Pat. No. 4,000,093, Nicol, et al., issued Dec.28, 1976; U.S. Pat. No. 4,702,857 Gosselink, issued Oct. 27, 1987; U.S.Pat. No. 4,968,451, Scheibel et al., issued November 6; U.S. Pat. No.4,702,857, Gosselink, issued Oct. 27, 1987; U.S. Pat. No. 4,711,730,Gosselink et al., issued Dec. 8, 1987, U.S. Pat. No. 4,721,580,Gosselink, issued Jan. 26, 1988; U.S. Pat. No. 4,877,896, Maldonado etal., issued Oct. 31, 1989; U.S. Pat. No. 4,956,447, Gosselink et al.,issued Sep. 11, 1990; U.S. Pat. No. 5,415,807 Gosselink et al., issuedMay 16, 1995; European Patent Application 0 219 048, published Apr. 22,1987 by Kud, et al.

Further suitable soil release agents are described in U.S. Pat. No.4,201,824, Violland et al.; U.S. Pat. No. 4,240,918 Lagasse et al.; U.S.Pat. No. 4,525,524 Tung et al.; U.S. Pat. No. 4,579,681, Ruppert et al.;U.S. Pat. Nos. 4,240,918; 4,787,989; 4,525,524; EP 279,134 A, 1988, toRhone-Poulenc Chemie; EP 457,205 A to BASF (1991); and DE 2,335,044 toUnilever N. V., 1974 all incorporated herein by reference.

Commercially available soil release agents include the METOLOSE SM100,METOLOSE SM200 manufactured by Shin-etsu Kagaku Kogyo K.K., SOKALAN typeof material, e.g., SOKALAN HP-22, available from BASF (Germany), ZELCON5126 (from Dupont) and MILEASE T (from ICI).

Bactericides

Examples of bactericides used in the compositions of this inventioninclude glutaraldehyde, formaldehyde, 2-bromo-2-nitro-propane-1,3-diolsold by Inolex Chemicals, located in Philadelphia, Pa., under the tradename Bronopol®, and a mixture of 5-chloro-2-methyl4-isothiazoline-3-oneand 2-methyl4-isothiazoline-3-one sold by Rohm and Haas Company underthe trade name Kathon 1 to 1,000 ppm by weight of the agent.

Perfume

The present invention can contain a perfume. Suitable perfumes aredisclosed in U.S. Pat. No. 5,500,138, said patent being incorporatedherein by reference. As used herein, perfume includes fragrant substanceor mixture of substances including natural (i.e., obtained by extractionof flowers, herbs, leaves, roots, barks, wood, blossoms or plants),artificial (i.e., a mixture of different nature oils or oilconstituents) and synthetic (i.e., synthetically produced) odoriferoussubstances. Such materials are often accompanied by auxiliary materials,such as fixatives, extenders, stabilizers and solvents. Theseauxiliaries are also included within the meaning of “perfume”, as usedherein. Typically, perfumes are complex mixtures of a plurality oforganic compounds.

The range of the natural raw substances can embrace not onlyreadily-volatile, but also moderately-volatile and slightly-volatilecomponents and that of the synthetics can include representatives frompractically all classes of fragrant substances, as will be evident fromthe following illustrative compilation: natural products, such as treemoss absolute, basil oil, citrus fruit oils (such as bergamot oil,mandarin oil, etc.), mastix absolute, myrtle oil, palmarosa oil,patchouli oil, petitgrain oil Paraguay, wormwood oil, alcohols, such asfarnesol, geraniol, linalool, nerol, phenylethyl alcohol, rhodinol,cinnamic alcohol, aldehydes, such as citral, Helional™,alpha-hexyl-cinnamaldehyde, hydroxycitronellal, Lilial™(p-tert-butyl-alpha -methyldihydrocinnamaldehyde),methyinonylacetaldehyde, ketones, such as allylionone, alpha-ionone,beta-ionone, isoraldein (isomethyl-alpha-ionone), methylionone, esters,such as allyl phenoxyacetate, benzyl salicylate, cinnamyl propionate,citronellyl acetate, citronellyl ethoxolate, decyl acetate,dimethylbenzylcarbinyl acetate, dimethylbenzylcarbinyl butyrate, ethylacetoacetate, ethyl acetylacetate, hexenyl isobutyrate, linalyl acetate,methyl dihydrojasmonate, styrallyl acetate, vetiveryl acetate, etc.,lactones, such as gamma-undecalactone, various components often used inperfumery, such as musk ketone, indole, p-menthane-8-thiol-3-one, andmethyl-eugenol. Likewise, any conventional fragrant acetal or ketalknown in the art can be added to the present composition as an optionalcomponent of the conventionally formulated perfume (c). Suchconventional fragrant acetals and ketals include the well-known methyland ethyl acetals and ketals, as well as acetals or ketals based onbenzaldehyde, those comprising phenylethyl moieties, or more recentlydeveloped specialties such as those described in a United States Patententitled “Acetals and Ketals of Oxo-Tetralins and Oxo-Indanes, see U.S.Pat. No. 5,084,440, issued Jan. 28, 1992, assigned to Givaudan Corp. Ofcourse, other recent synthetic specialties can be included in theperfume compositions for fully-formulated fabric softening compositions.These include the enol ethers of alkyl-substituted oxo-tetralins andoxo-indanes as described in U.S. Pat. 5,332,725, Jul. 26, 1994, assignedto Givaudan; or Schiff Bases as described in U.S. Pat. 5,264,615, Dec.9, 1991, assigned to Givaudan.

The perfumes useful in the present invention compositions aresubstantially free of halogenated materials and nitromusks.

Perfume can be present at a level of from 0% to 10%, preferably from0.1% to 5%, and more preferably from 0.2% to 3%, by weight of thefinished composition. Fabric care compositions of the present inventionprovide improved fabric perfume deposition.

Crystal Growth Inhibitor Component

The fabric care compositions of the present invention can furthercontain a crystal growth inhibitor component, preferably anorganodiphosphonic acid component, incorporated preferably at a level offrom 0.01% to 5%, more preferably from 0.1% to 2% by weight of thecompositions.

By organo diphosphonic acid it is meant herein an organo diphosphonicacid which does not contain nitrogen as part of its chemical structure.This definition therefore excludes the organo aminophosphonates, whichhowever may be included in compositions of the invention as heavy metalion sequestrant components.

The organo diphosphonic acid is preferably a C₁-C₄ diphosphonic acid,more preferably a C₂ diphosphonic acid, such as ethylene diphosphonicacid, or most preferably ethane 1-hydroxy-1,1-diphosphonic acid (HEDP)and may be present in partially or fully ionized form, particularly as asalt or complex.

Enzyme

The compositions and processes herein can optionally employ one or moreenzymes such as lipases, proteases, cellulase, amylases and peroxidases.A preferred enzyme for use herein is a cellulase enzyme. Indeed, thistype of enzyme will further provide a color care benefit to the treatedfabric. Cellulases usable herein include both bacterial and fungaltypes, preferably having a pH optimum between 5 and 9.5. U.S. Pat. No.4,435,307 discloses suitable fungal cellulases from Humicola insolens orHumicola strain DSM1800 or a cellulase 212-producing fungus belonging tothe genus Aeromonas, and cellulase extracted from the hepatopancreas ofa marine mollusk, Dolabella Auricula Solander. Suitable cellulases arealso disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.CAREZYME® and CELLUZYME® (Novo) are especially useful. Other suitablecellulases are also disclosed in WO 91/17243 to Novo, WO 96134092, WO96134945 and EP-A-0,739,982. In practical terms for current commercialpreparations, typical amounts are up to 5 mg by weight, more typically0.0001 mg to 3 mg, of active enzyme per gram of the detergentcomposition. Stated otherwise, the compositions herein will typicallycomprise from 0.001% to 5%, preferably 0.01%-1% by weight of acommercial enzyme preparation. In the particular cases where activity ofthe enzyme preparation can be defined otherwise such as with cellulases,corresponding activity units can also be used (e.g. CEVU or cellulaseEquivalent Viscosity Units). For instance, the compositions of thepresent invention can contain cellulase enzymes at a level equivalent toan activity from 0.5 to 1000 CEVU/gram of composition. Cellulase enzymepreparations used for the purpose of formulating the compositions ofthis invention typically have an activity comprised between 1,000 and10,000 CEVU/gram in liquid or solid form.

Other Optional Ingredients

The present invention can include optional components conventionallyused in textile treatment compositions, for example: brighteners,colorants; surfactants; anti-shrinkage agents; fabric crisping agents;spotting agents; germicides; fungicides; anti-oxidants such as butylatedhydroxy toluene, anti-corrosion agents, antifoam agents, and the like.

The present invention can also include other compatible ingredients,including those as disclosed in WO96/02625, WO96/21714, and WO96/21715,and dispersible polyolefin such as Velustrol® as disclosed in co-pendingapplication PCT/US 97/01644, and the like. The present invention canalso contain optional chelating agents.

Applications

The compositions of the invention are suitable for use in any steps ofthe domestic treatment, that is as a pre-treatment composition, as awash additive as a composition suitable for use in the rinse-cycle ofthe laundry cycle or applied on a dryer-sheet. Obviously, for thepurpose of the invention, multiple applications can be made such astreating the fabric with a pre-treatment composition of the inventionand also thereafter with a composition of the invention suitable for usein the rinse cycle and/or suitable for use as a dryer-sheet. Thecompositions of the invention may also be in a spray, foam, or aerosolform which for example can be suitable for use while ironing, or appliedon the surfaces of the tumble dryer.

Surfactant System

The fabric care compositions when formulated as laundry softeningthrough-the-wash compositions according to the present inventiongenerally comprise a surfactant system wherein the surfactant can beselected from nonionic and/or anionic and/or cationic and/or ampholyticand/or zwitterionic and/or semi-polar surfactants.

The surfactant is typically present at a level of from 0.1% to 60% byweight. More preferred levels of incorporation are 1% to 35% by weight,most preferably from 1% to 30% by weight of fabric care compositions inaccord with the invention.

The surfactant is preferably formulated to be compatible with enzymecomponents present in the composition. In liquid or gel compositions thesurfactant is most preferably formulated such that it promotes, or atleast does not degrade, the stability of any enzyme in thesecompositions.

Preferred surfactant systems to be used according to the presentinvention comprise as a surfactant one or more of the nonionic and/oranionic surfactants described herein.

Polyethylene, polypropylene, and polybutylene oxide condensates of alkylphenols are suitable for use as the nonionic surfactant of thesurfactant systems of the present invention, with the polyethylene oxidecondensates being preferred. These compounds include the condensationproducts of alkyl phenols having an alkyl group containing from about 6to about 14 carbon atoms, preferably from about 8 to about 14 carbonatoms, in either a straight-chain or branched-chain configuration withthe alkylene oxide. In a preferred embodiment, the ethylene oxide ispresent in an amount equal to from about 2 to about 25 moles, morepreferably from about 3 to about 15 moles, of ethylene oxide per mole ofalkyl phenol. Commercially available nonionic surfactants of this typeinclude Igepal™ CO-630, marketed by the GAF Corporation; and Triton™X45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company.These surfactants are commonly referred to as alkylphenol alkoxylates(e.g., alkyl phenol ethoxylates).

The condensation products of primary and secondary aliphatic alcoholswith from about 1 to about 25 moles of ethylene oxide are suitable foruse as the nonionic surfactant of the nonionic surfactant systems of thepresent invention. The alkyl chain of the aliphatic alcohol can eitherbe straight or branched, primary or secondary, and generally containsfrom about 8 to about 22 carbon atoms. Preferred are the condensationproducts of alcohols having an alkyl group containing from about 8 toabout 20 carbon atoms, more preferably from about 10 to about 18 carbonatoms, with from about 2 to about 10 moles of ethylene oxide per mole ofalcohol. About 2 to about 7 moles of ethylene oxide and most preferablyfrom 2 to 5 moles of ethylene oxide per mole of alcohol are present insaid condensation products. Examples of commercially available nonionicsurfactants of this type include Tergitol™ 15-S-9 (the condensationproduct of C₁ ₁-C₁₅ linear alcohol with 9 moles ethylene oxide),Tergitol™ 24-L-6 NMW (the condensation product of C₁₂-C₁₄ primaryalcohol with 6 moles ethylene oxide with a narrow molecular weightdistribution), both marketed by Union Carbide Corporation; Neodol™ 45-9(the condensation product of C₁₄-C₁₅ linear alcohol with 9 moles ofethylene oxide), Neodol™ 23-3 (the condensation product of C₁₂-C₁₃linear alcohol with 3.0 moles of ethylene oxide), Neodol™ 45-7 (thecondensation product of C₁₄-C₁₅ linear alcohol with 7 moles of ethyleneoxide), Neodol™ 45-5 (the condensation product of C₁₄-C₁₅ linear alcoholwith 5 moles of ethylene oxide) marketed by Shell Chemical Company,Kyro™ EOB (the condensation product of C₁₃-C₁₅ alcohol with 9 molesethylene oxide), marketed by The Procter & Gamble Company, and GenapolLA O3O or O5O (the condensation product of C₁₂-C₁₄ alcohol with 3 or 5moles of ethylene oxide) marketed by Hoechst. Preferred range of HLB inthese products is from 8-11 and most preferred from 8-10.

Also useful as the nonionic surfactant of the surfactant systems of thepresent invention are the alkylpolysaccharides disclosed in U.S. Pat.No. 4,565,647, Lienado, issued Jan. 21, 1986, having a hydrophobic groupcontaining from about 6 to about 30 carbon atoms, preferably from about10 to about 16 carbon atoms and a polysaccharide, e.g. a polyglycoside,hydrophilic group containing from about 1.3 to about 10, preferably fromabout 1.3 to about 3, most preferably from about 1.3 to about 2.7saccharide units. Any reducing saccharide containing 5 or 6 carbon atomscan be used, e.g., glucose, galactose and galactosyl moieties can besubstituted for the glucosyl moieties (optionally the hydrophobic groupis attached at the 2-, 3-, 4-, etc. positions thus giving a glucose orgalactose as opposed to a glucoside or galactoside). The intersaccharidebonds can be, e.g., between the one position of the additionalsaccharide units and the 2-, 3, 4-, and/or 6- positions on the precedingsaccharide units. The preferred alkylpolyglycosides have the formulaR²O(C_(n)H_(2n)O)_(t)(glycosyl)_(x)wherein R² is selected from the group consisting of alkyl, alkylphenyl,hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which thealkyl groups contain from about 10 to about 18, preferably from about 12to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 toabout 10, preferably 0; and x is from about 1.3 to about 10, preferablyfrom about 1.3 to about 3, most preferably from about 1.3 to about 2.7.The glycosyl is preferably derived from glucose. To prepare thesecompounds, the alcohol or alkylpolyethoxy alcohol is formed first andthen reacted with glucose, or a source of glucose, to form the glucoside(attachment at the 1-position). The additional glycosyl units can thenbe attached between their 1-position and the preceding glycosyl units2-, 3-, 4- and/or 6-position, preferably predominately the 2-position.

The condensation products of ethylene oxide with a hydrophobic baseformed by the condensation of propylene oxide with propylene glycol arealso suitable for use as the additional nonionic surfactant systems ofthe present invention. The hydrophobic portion of these compounds willpreferably have a molecular weight of from about 1500 to about 1800 andwill exhibit water insolubility. The addition of polyoxyethylenemoieties to this hydrophobic portion tends to increase the watersolubility of the molecule as a whole, and the liquid character of theproduct is retained up to the point where the polyoxyethylene content isabout 50% of the total weight of the condensation product, whichcorresponds to condensation with up to about 40 moles of ethylene oxide.Examples of compounds of this type include certain of thecommercially-available Plurafac™ LF404 and Pluronic™ surfactants,marketed by BASF.

Also suitable for use as the nonionic surfactant of the nonionicsurfactant system of the present invention, are the condensationproducts of ethylene oxide with the product resulting from the reactionof propylene oxide and ethylenediamine. The hydrophobic moiety of theseproducts consists of the reaction product of ethylenediamine and excesspropylene oxide, and generally has a molecular weight of from about 2500to about 3000. This hydrophobic moiety is condensed with ethylene oxideto the extent that the condensation product contains from about 40% toabout 80% by weight of polyoxyethylene and has a molecular weight offrom about 5,000 to about 11,000. Examples of this type of nonionicsurfactant include certain of the commercially available Tetronic™compounds, marketed by BASF.

Preferred for use as the nonionic surfactant of the surfactant systemsof the present invention are polyethylene oxide condensates of alkylphenols, condensation products of primary and secondary aliphaticalcohols with from about 1 to about 25 moles of ethylene oxide,alkylpolysaccharides, and mixtures thereof. Most preferred are C₈-C₁₄alkyl phenol ethoxylates having from 3 to 15 ethoxy groups and C₈-C₁₈alcohol ethoxylates (preferably C₁₀ avg.) having from 2 to 10 ethoxygroups, and mixtures thereof.

Highly preferred nonionic surfactants are polyhydroxy fatty acid amidesurfactants of the formula.

wherein R¹ is H, or R¹ is C₁₋₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxypropyl or a mixture thereof, R² is C₅₋₃₁ hydrocarbyl, and Z is apolyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3hydroxyls directly connected to the chain, or an alkoxylated derivativethereof. Preferably, R¹ is methyl, R² is a straight C₁₁₋₁₅ alkyl orC₁₆₋₁₈ alkyl or alkenyl chain such as coconut alkyl or mixtures thereof,and Z is derived from a reducing sugar such as glucose, fructose,maltose, lactose, in a reductive amination reaction.

Suitable anionic surfactants to be used are linear alkyl benzenesulfonate, alkyl ester sulfonate surfactants including linear esters ofC₈-C₂₀ carboxylic acids (i.e., fatty acids) which are sulfonated withgaseous SO₃ according to “The Journal of the American Oil ChemistsSociety”, 52 (1975), pp. 323-329. Suitable starting materials wouldinclude natural fatty substances as derived from tallow, palm oil, etc.

The preferred alkyl ester sulfonate surfactant, especially for laundryapplications, comprise alkyl ester sulfonate surfactants of thestructural formula:

wherein R³ is a C₈-C₂₀ hydrocarbyl, preferably an alkyl, or combinationthereof, R⁴ is a C₁-C₆ hydrocarbyl, preferably an alkyl, or combinationthereof, and M is a cation which forms a water soluble salt with thealkyl ester sulfonate. Suitable salt-forming cations include metals suchas sodium, potassium, and lithium, and substituted or unsubstitutedammonium cations, such as monoethanolamine, diethanolamine, andtriethanolamine. Preferably, R³ is C₁₀-C₁₆ alkyl, and R⁴ is methyl,ethyl or isopropyl. Especially preferred are the methyl ester sulfonateswherein R³ is C₁₀-C₁₆ alkyl.

Other suitable anionic surfactants include the alkyl sulfate surfactantswhich are water soluble salts or acids of the formula ROSO₃M wherein Rpreferably is a C₁₀-C₂₄ hydrocarbyl, preferably an alkyl or hydroxyalkylhaving a C₁₀-C₂₀ alkyl component, more preferably a C₁₂-C₁₈ alkyl orhydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g.sodium, potassium, lithium), or ammonium or substituted ammonium (e.g.methyl-, dimethyl-, and trimethyl ammonium cations and quaternaryammonium cations such as tetramethyl-ammonium and dimethyl piperdiniumcations and quaternary ammonium cations derived from alkylamines such asethylamine, diethylamine, triethylamine, and mixtures thereof, and thelike). Typically, alkyl chains of C₁₂-C₁₆ are preferred for lower washtemperatures (e.g. below about 50° C.) and C₁₆₋₁₈ alkyl chains arepreferred for higher wash temperatures (e.g. above about 50° C.).

Other anionic surfactants useful for detersive purposes can also beincluded in the fabric care compositions of the present invention. Thesecan include salts (including, for example, sodium, potassium, ammonium,and substituted ammonium salts such as mono-, di- and triethanolaminesalts) of soap, C₈-C₂₂ primary of secondary alkanesulfonates, C₈-C₂₄olefinsulfonates, sulfonated polycarboxylic acids prepared bysulfonation of the pyrolyzed product of alkaline earth metal citrates,e.g., as described in British patent specification No. 1,082,179, C₈-C₂₄alkylpolyglycolethersulfates (containing up to 10 moles of ethyleneoxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fattyoleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates,paraffin sulfonates, alkyl phosphates, isethionates such as the acylisethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates,monoesters of sulfosuccinates (especially saturated and unsaturatedC₁₂-C₁₈ monoesters) and diesters of sulfosuccinates (especiallysaturated and unsaturated C₆-C₁₂ diesters), acyl sarcosinates, sulfatesof alkylpolysaccharides such as the sulfates of alkylpolyglucoside (thenonionic nonsulfated compounds being described below), branched primaryalkyl sulfates, and alkyl polyethoxy carboxylates such as those of theformula RO(CH₂CH₂O)_(k)—CH₂COO—M+ wherein R is a C₈-C₂₂ alkyl, k is aninteger from 1 to 10, and M is a soluble salt-forming cation. Resinacids and hydrogenated resin acids are also suitable, such as rosin,hydrogenated rosin, and resin acids and hydrogenated resin acids presentin or derived from tall oil.

Further examples are described in “Surface Active Agents and Detergents”(Vol. I and II by Schwartz, Perry and Berch). A variety of suchsurfactants are also generally disclosed in U.S. Pat. No. 3,929,678,issued Dec. 30, 1975 to Laughlin, et al. at Column 23, line 58 throughColumn 29, line 23 (herein incorporated by reference).

When included therein, the laundry detergent compositions of the presentinvention typically comprise from about 1% to about 40%, preferably fromabout 3% to about 20% by weight of such anionic surfactants.

Highly preferred anionic surfactants include alkyl alkoxylated sulfatesurfactants hereof are water soluble salts or acids of the formulaRO(A)_(m)SO3M wherein R is an unsubstituted C₁₀-C₂₄ alkyl orhydroxyalkyl group having a C₁₀-C₂₄ alkyl component, preferably aC₁₂-C₂₀ alkyl or hydroxyalkyl, more preferably C₁₂-C₁₈ alkyl orhydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero,typically between about 0.5 and about 6, more preferably between about0.5 and about 3, and M is H or a cation which can be, for example, ametal cation (e.g., sodium, potassium, lithium, calcium, magnesium,etc.), ammonium or substituted-ammonium cation. Alkyl ethoxylatedsulfates as well as alkyl propoxylated sulfates are contemplated herein.Specific examples of substituted ammonium cations include methyl-,dimethyl, trimethyl-ammonium cations and quaternary ammonium cationssuch as tetramethyl-ammonium and dimethyl piperdinium cations and thosederived from alkylamines such as ethylamine, diethylamine,triethylamine, mixtures thereof, and the like. Exemplary surfactants areC₁₂-C₁₈ alkyl polyethoxylate (1.0) sulfate (C₁₂-C₁₈E(1.0)M), C₁₂-C₁₈alkyl polyethoxylate (2.25) sulfate (C₁₂-C₁₈E(2.25)M), C₁₂-C₁₈ alkylpolyethoxylate (3.0) sulfate (C₁₂-C₁₈E(3.0)M), and C₁₂-C₁₈ alkylpolyethoxylate (4.0) sulfate (C₁₂-C₁₈E(4.0)M), wherein M is convenientlyselected from sodium and potassium.

The fabric care compositions of the present invention may also containcationic, ampholytic, zwitterionic, and semi-polar surfactants, as wellas the nonionic and/or anionic surfactants other than those alreadydescribed herein.

Cationic detersive surfactants suitable for use in the fabric carecompositions of the present invention are those having one long-chainhydrocarbyl group. Examples of such cationic surfactants include theammonium surfactants such as alkyltrimethylammonium halogenides, andthose surfactants having the formula:[R²(OR³)_(y)][R⁴(OR³)_(y)]₂R⁵N+X−wherein R² is an alkyl or alkyl benzyl group having from about 8 toabout 18 carbon atoms in the alkyl chain, each R³ is selected from thegroup consisting of —CH₂CH₂—, —CH₂CH(CH₃)—, —CH₂CH(CH₂OH)—, —CH₂CH₂CH₂—,and mixtures thereof; each R⁴ is selected from the group consisting ofC₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, benzyl ring structures formed byjoining the two R⁴ groups, —CH₂CHOH—CHOHCOR⁶CHOHCH₂OH wherein R⁶ is anyhexose or hexose polymer having a molecular weight less than about 1000,and hydrogen when y is not 0; R⁵ is the same as R⁴ or is an alkyl chainwherein the total number of carbon atoms of R² plus R⁵ is not more thanabout 18; each y is from 0 to about 10 and the sum of the y values isfrom 0 to about 15; and X is any compatible anion.

Quaternary ammonium surfactant suitable for the present invention hasthe formula (I):

whereby R1 is a short chainlength alkyl (C6-C10) or alkylamidoalkyl ofthe formula (II):

y is 2-4, preferably 3.whereby R2 is H or a C1-C3 alkyl,whereby x is 0-4, preferably 0-2, most preferably 0,whereby R3, R4 and R5 are either the same or different and can be eithera short chain alkyl (C1-C3) or alkoxylated alkyl of the formula III,whereby X⁻ is a counterion, preferably a halide, e.g. chloride ormethylsulfate.

R6 is C₁-C₄ and z is 1 or 2.

Preferred quat ammonium surfactants are those as defined in formula Iwhereby R₁ is C₈, C₁₀ or mixtures thereof, x=o, R₃, R₄=CH₃ andR₅=CH₂CH₂OH.

Highly preferred cationic surfactants are the water-soluble quaternaryammonium compounds useful in the present composition having the formula:R₁R₂R₃R₄N⁺X⁻  (i)wherein R₁ is C₈-C₁₆ alkyl, each of R₂, R₃ and R₄ is independently C₁-C₄alkyl, C₁-C₄ hydroxy alkyl, benzyl, and −(C₂H₄₀)_(x)H where x has avalue from 2 to 5, and X is an anion. Not more than one of R₂, R₃ or R₄should be benzyl.

The preferred alkyl chain length for R₁ is C₁₂-C₁₅ particularly wherethe alkyl group is a mixture of chain lengths derived from coconut orpalm kernel fat or is derived synthetically by olefin build up or OXOalcohols synthesis. Preferred groups for R₂R₃ and R₄ are methyl andhydroxyethyl groups and the anion X may be selected from halide,methosulphate, acetate and phosphate ions. Examples of suitablequaternary ammonium compounds of formulae (i) for use herein are:

-   -   coconut trimethyl ammonium chloride or bromide;    -   coconut methyl dihydroxyethyl ammonium chloride or bromide;    -   decyl triethyl ammonium chloride;    -   decyl dimethyl hydroxyethyl ammonium chloride or bromide;    -   C₁₂-₁₅ dimethyl hydroxyethyl ammonium chloride or bromide;    -   coconut dimethyl hydroxyethyl ammonium chloride or bromide;    -   myristyl trimethyl ammonium methyl sulphate;    -   lauryl dimethyl benzyl ammonium chloride or bromide;    -   lauryl dimethyl (ethenoxy)₄ ammonium chloride or bromide;    -   choline esters (compounds of formula (i) wherein R₁ is        di-alkyl imidazolines [compounds of formula (i)].

Other cationic surfactants useful herein are also described in U.S. Pat.No. 4,228,044, Cambre, issued Oct. 14, 1980 and in European PatentApplication EP 000,224.

When included therein, the fabric care compositions of the presentinvention typically comprise from 0.2% to about 25%, preferably fromabout 1% to about 8% by weight of such cationic surfactants.

Ampholytic surfactants are also suitable for use in the fabric carecompositions of the present invention. These surfactants can be broadlydescribed as aliphatic derivatives of secondary or tertiary amines, oraliphatic derivatives of heterocyclic secondary and tertiary amines inwhich the aliphatic radical can be straight- or branched-chain. One ofthe aliphatic substituents contains at least about 8 carbon atoms,typically from about 8 to about 18 carbon atoms, and at least onecontains an anionic water-solubilizing group, e.g. carboxy, sulfonate,sulfate. See U.S. Pat. No. 3,929,678 to Laughlin et al., issued Dec. 30,1975 at column 19, lines 18-35, for examples of ampholytic surfactants.When included therein, the fabric care compositions of the presentinvention typically comprise from 0.2% to about 15%, preferably fromabout 1% to about 10% by weight of such ampholytic surfactants.

Zwitterionic surfactants are also suitable for use in fabric carecompositions. These surfactants can be broadly described as derivativesof secondary and tertiary amines, derivatives of heterocyclic secondaryand tertiary amines, or derivatives of quaternary ammonium, quaternaryphosphonium or tertiary sulfonium compounds. See U.S. Pat. No. 3,929,678to Laughlin et al., issued Dec. 30, 1975 at column 19, line 38 throughcolumn 22, line 48, for examples of zwitterionic surfactants.

When included therein, the fabric care compositions of the presentinvention typically comprise from 0.2% to about 15%, preferably fromabout 1% to about 10% by weight of such zwitterionic surfactants.

Semi-polar nonionic surfactants are a special category of nonionicsurfactants which include water-soluble amine oxides containing onealkyl moiety of from about 10 to about 18 carbon atoms and 2 moietiesselected from the group consisting of alkyl groups and hydroxyalkylgroups containing from about 1 to about 3 carbon atoms; water-solublephosphine oxides containing one alkyl moiety of from about 10 to about18 carbon atoms and 2 moieties selected from the group consisting ofalkyl groups and hydroxyalkyl groups containing from about 1 to about 3carbon atoms; and water-soluble sulfoxides containing one alkyl moietyof from about 10 to about 18 carbon atoms and a moiety selected from thegroup consisting of alkyl and hydroxyalkyl moieties of from about 1 toabout 3 carbon atoms.

Semi-polar nonionic detergent surfactants include the amine oxidesurfactants having the formula

wherein R³ is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixturestherof containing from about 8 to about 22 carbon atoms; R⁴ is analkylene or hydroxyalkylene group containing from about 2 to about 3carbon atoms or mixtures thereof; x is from 0 to about 3; and each R⁵ isan alkyl or hydroxyalkyl group containing from about 1 to about 3 carbonatoms or a polyethylene oxide group containing from about 1 to about 3ethylene oxide groups. The R⁵ groups can be attached to each other,e.g., through an oxygen or nitrogen atom, to form a ring structure.

These amine oxide surfactants in particular include C₁₀-C₁₈ alkyldimethyl amine oxides and C₈-C₁₂ alkoxy ethyl dihydroxy ethyl amineoxides. When included therein, the cleaning compositions of the presentinvention typically comprise from 0.2% to about 15%, preferably fromabout 1% to about 10% by weight of such semi-polar nonionic surfactants.

The fabric care composition of the present invention may furthercomprise a cosurfactant selected from the group of primary or tertiaryamines. Suitable primary amines for use herein include amines accordingto the formula R₁NH₂ wherein R₁ is a C₆-C₁₂, preferably C₆-C₁₀ alkylchain or R₄X(CH₂)_(n), X is —O—,—C(O)NH— or —NH—R₄ is a C₆-C₁₂ alkylchain n is between 1 to 5, preferably 3. R₁ alkyl chains may be straightor branched and may be interrupted with up to 12, preferably less than 5ethylene oxide moieties. Preferred amines according to the formulaherein above are n-alkyl amines. Suitable amines for use herein may beselected from 1-hexylamine, 1-octylamine, 1-decylamine and laurylamine.Other preferred primary amines include C8-C10 oxypropylamine,octyloxypropylamine, 2-ethylhexyl-oxypropylamine, lauryl amidopropylamine and amido propylamine.

Suitable tertiary amines for use herein include tertiary amines havingthe formula R₁R₂R₃N wherein R1 and R2 are C₁-C₈ alkylchains or

R₃ is either a C₆-C₁₂, preferably C₆-C₁₀ alkyl chain, or R₃ isR₄X(CH₂)_(n), whereby X is —O—, —C(O)NH— or —NH—R₄ is a C₄-C₁₂, n isbetween 1 to 5, preferably 2-3. R₅ is H or C₁-C₂ alkyl and x is between1 to 6. R ₃ and R₄ may be linear or branched ; R₃ alkyl chains may beinterrupted with up to 12, preferably less than 5, ethylene oxidemoieties.

Preferred tertiary amines are R₁R₂R₃N where R1 is a C6-C12 alkyl chain,R2 and R3 are C1-C3 alkyl or

where R5 is H or CH3 and x=1-2.

Also preferred are the amidoamines of the formula:

wherein R₁ is C₆-C₁₂ alkyl; n is 2-4,preferably n is 3; R₂ and R₃ is C₁-C₄

Most preferred amines of the present invention include 1-octylamine,1-hexylamine, 1-decylamine, 1-dodecylamine,C8-10oxypropylamine, N coco1-3diaminopropane, coconutalkyldimethylamine, lauryldimethylamine,lauryl bis(hydroxyethyl)amine, coco bis(hydroxyethyl)amine, lauryl amine2 moles propoxylated, octyl amine 2 moles propoxylated, laurylamidopropyl-dimethylamine, C8-10 amidopropyldimethylamine and C10amidopropyl-dimethylamine.

The most preferred amines for use in the compositions herein are1-hexylamine, 1-octylamine, 1-decylamine, 1-dodecylamine. Especiallydesirable are n-dodecyldimethylamine andbishydroxyethylcoconutalkylamine and oleylamine 7 times ethoxylated,lauryl amido propylamine and cocoamido propylamine.

Bleaching Agent

Additional optional detergent ingredients that can be included in thefabric care compositions when formulated as laundry softeningthrough-the-wash compositions of the present invention include bleachingagents such as hydrogen peroxide, PB1, PB4 and percarbonate with aparticle size of 400-800 microns. These bleaching agent components caninclude one or more oxygen bleaching agents and, depending upon thebleaching agent chosen, one or more bleach activators. When presentoxygen bleaching compounds will typically be present at levels of fromabout 1% to about 25%.

The bleaching agent component for use herein can be any of the bleachingagents useful for fabric care compositions including oxygen bleaches aswell as others known in the art. The bleaching agent suitable for thepresent invention can be an activated or non-activated bleaching agent.

One category of oxygen bleaching agent that can be used encompassespercarboxylic acid bleaching agents and salts thereof. Suitable examplesof this class of agents include magnesium monoperoxyphthalatehexahydrate, the magnesium salt of meta-chloro perbenzoic acid,4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.Such bleaching agents are disclosed in U.S. Pat. No. 4,483,781, U.S.patent application Ser. No. 740,446, European Patent Application0,133,354 and U.S. Pat. No. 4,412,934. Highly preferred bleaching agentsalso include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S.Pat. 4,634,551.

Another category of bleaching agents that can be used encompasses thehalogen bleaching agents. Examples of hypohalite bleaching agents, forexample, include trichloro isocyanuric acid and the sodium and potassiumdichloroisocyanurates and N-chloro and N-bromo alkane sulphonamides.Such materials are normally added at 0.5-10% by weight of the finishedproduct, preferably 1-5% by weight.

The hydrogen peroxide releasing agents can be used in combination withbleach activators such as tetraacetylethylenediamine (TAED),nonanoyloxy-benzene-sulfonate (NOBS, described in U.S. Pat. No.4,412,934), 3,5,-trimethylhexanoloxybenzenesulfonate (ISONOBS, describedin EP 120,591) or pentaacetylglucose (PAG)or Phenolsulfonate ester ofN-nonanoyl-6-aminocaproic acid (NACA-OBS, described in WO94/28106),which are perhydrolyzed to form a peracid as the active bleachingspecies, leading to improved bleaching effect. Also suitable activatorsare acylated citrate esters such as disclosed in Copending EuropeanPatent Application No. 91870207.7 and unsymetrical acyclic imide bleachactivator of the following formula as disclosed in the Procter & Gambleco-pending patent applications U.S. Ser. No. 60/022,786 (filed Jul. 30,1996) and No. 60/028,122 (filed Oct. 15, 1996):

wherein R₁ is a C₇-C₁₃ linear or branched chain saturated or unsaturatedalkyl group, R₂ is a C₁-C₈, linear or branched chain saturated orunsaturated alkyl group and R₃ is a C₁-C₄ linear or branched chainsaturated or unsaturated alkyl group.

Useful bleaching agents, including peroxyacids and bleaching systemscomprising bleach activators and peroxygen bleaching compounds for usein detergent compositions according to the invention are described inour co-pending applications U.S. Ser. No. 08/136,626, PCT/US95/07823,WO95/27772, WO95/27773, WO95127774 and WO95/27775.

The hydrogen peroxide may also be present by adding an enzymatic system(i.e. an enzyme and a substrate therefore) which is capable ofgenerating hydrogen peroxide at the beginning or during the washingand/or rinsing process. Such enzymatic systems are disclosed in EPPatent Application 91202655.6 filed Oct. 9, 1991.

Metal-containing catalysts for use in bleach compositions, includecobalt-containing catalysts such as Pentaamine acetate cobalt(III) saltsand manganese-containing catalysts such as those described in EPA 549271; EPA 549 272; EPA 458 397; U.S. Pat. No. 5,246,621; EPA 458 398;U.S. Pat. Nos. 5,194,416 and 5,114,611. Bleaching composition comprisinga peroxy compound, a manganese-containing bleach catalyst and achelating agent is described in the patent application No 94870206.3.

Bleaching agents other than oxygen bleaching agents are also known inthe art and can be utilized herein. One type of non-oxygen bleachingagent of particular interest includes photoactivated bleaching agentssuch as the sulfonated zinc and/or aluminum phthalocyanines. Thesematerials can be deposited upon the substrate during the washingprocess. Upon irradiation with light, in the presence of oxygen, such asby hanging clothes out to dry in the daylight, the sulfonated zincphthalocyanine is activated and, consequently, the substrate isbleached. Preferred zinc phthalocyanine and a photoactivated bleachingprocess are described in U.S. Pat. No. 4,033,718. Typically, detergentcompositions will contain about 0.025% to about 1.25%, by weight, ofsulfonated zinc phthalocyanine.

Builder System

The fabric care compositions when formulated as laundry softeningthrough-the-wash compositions according to the present invention mayfurther comprise a builder system. Any conventional builder system issuitable for use herein including aluminosilicate materials, silicates,polycarboxylates, alkyl- or alkenyl-succinic acid and fatty acids,materials such as ethylenediamine tetraacetate, diethylene triaminepentamethyleneacetate, metal ion sequestrants such asaminopolyphosphonates, particularly ethylenediamine tetramethylenephosphonic acid and diethylene triamine pentamethylenephosphonic acid.Phosphate builders can also be used herein.

Suitable builders can be an inorganic ion exchange material, commonly aninorganic hydrated aluminosilicate material, more particularly ahydrated synthetic zeolite such as hydrated zeolite A, X, B, HS or MAP.Another suitable inorganic builder material is layered silicate, e.g.SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate consisting ofsodium silicate (Na₂Si₂O₅).

Suitable polycarboxylates containing one carboxy group include lacticacid, glycolic acid and ether derivatives thereof as disclosed inBelgian Patent Nos. 831,368, 821,369 and 821,370. Polycarboxylatescontaining two carboxy groups include the water-soluble salts ofsuccinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid,diglycollic acid, tartaric acid, tartronic acid and fumaric acid, aswell as the ether carboxylates described in German Offenlegenschrift2,446,686, and 2,446,687 and U.S. Pat. No. 3,935,257 and the sulfinylcarboxylates described in Belgian Patent No. 840,623. Polycarboxylatescontaining three carboxy groups include, in particular, water-solublecitrates, aconitrates and citraconates as well as succinate derivativessuch as the carboxymethyloxysuccinates described in British Patent No.1,379,241, lactoxysuccinates described in Netherlands Application7205873, and the oxypolycarboxylate materials such as2-oxa-1,1,3-propane tricarboxylates described in British Patent No.1,387,447.

Polycarboxylates containing four carboxy groups include oxydisuccinatesdisclosed in British Patent No. 1,261,829, 1,1,2,2-ethanetetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propanetetracarboxylates. Polycarboxylates containing sulfo substituentsinclude the sulfosuccinate derivatives disclosed in British Patent Nos.1,398,421 and 1,398,422 and in U.S. Pat. No. 3,936,448, and thesulfonated pyrolysed citrates described in British Patent No. 1,082,179,while polycarboxylates containing phosphone substituents are disclosedin British Patent No. 1,439,000.

Alicyclic and heterocyclic polycarboxylates includecyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienidepentacarboxylates, 2,3,4,5-tetrahydro-furan-cis, cis,cis-tetracarboxylates, 2,5-tetrahydro-furan -cis - dicarboxylates,2,2,5,5-tetrahydrofuran-tetracarboxylates,1,2,3,4,5,6-hexane-hexacarboxylates and carboxymethyl derivatives ofpolyhydric alcohols such as sorbitol, mannitol and xylitol. Aromaticpoly-carboxylates include mellitic acid, pyromellitic acid and thephthalic acid derivatives disclosed in British Patent No. 1,425,343. Ofthe above, the preferred polycarboxylates are hydroxycarboxylatescontaining up to three carboxy groups per molecule, more particularlycitrates.

Preferred builder systems for use in the present compositions include amixture of a water-insoluble aluminosilicate builder such as zeolite Aor of a layered silicate (SKS-6), and a water-soluble carboxylatechelating agent such as citric acid. Other preferred builder systemsinclude a mixture of a water-insoluble aluminosilicate builder such aszeolite A, and a watersoluble carboxylate chelating agent such as citricacid. Preferred builder systems for use in liquid detergent compositionsof the present invention are soaps and polycarboxylates.

Other builder materials that can form part of the builder system for usein granular compositions include inorganic materials such as alkalimetal carbonates, bicarbonates, silicates, and organic materials such asthe organic phosphonates, amino polyalkylene phosphonates and aminopolycarboxylates. Other suitable water-soluble organic salts are thehomo- or co-polymeric acids or their salts, in which the polycarboxylicacid comprises at least two carboxyl radicals separated from each otherby not more than two carbon atoms Polymers of this type are disclosed inGB-A-1,596,756. Examples of such salts are polyacrylates of MW 2000-5000and their copolymers with maleic anhydride, such copolymers having amolecular weight of from 20,000 to 70,000, especially about 40,000.

Detergency builder salts are normally included in amounts of from 5% to80% by weight of the composition preferably from 10% to 70% and mostusually from 30% to 60% by weight.

Chelating Agents

The fabric care compositions when formulated as laundry softeningthrough-the-wash compositions herein may also optionally contain one ormore iron and/or manganese chelating agents. Such chelating agents canbe selected from the group consisting of amino carboxylates, aminophosphonates, polyfunctionally-substituted aromatic chelating agents andmixtures therein, all as hereinafter defined. Without intending to bebound by theory, it is believed that the benefit of these materials isdue in part to their exceptional ability to remove iron and manganeseions from washing solutions by formation of soluble chelates.

Amino carboxylates useful as optional chelating agents includeethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates,nitrilotriacetates, ethylenediamine tetraproprionates,triethylenetetra-aminehexacetates, diethylenetriaminepentaacetates, andethanoldiglycines, alkali metal, ammonium, and substituted ammoniumsalts therein and mixtures therein.

Amino phosphonates are also suitable for use as chelating agents in thecompositions of the invention when at lease low levels of totalphosphorus are permitted in detergent compositions, and includeethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred,these amino phosphonates to not contain alkyl or alkenyl groups withmore than about 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also usefulin the compositions herein. See U.S. Pat. No. 3,812,044, issued May 21,1974, to Connor et al. Preferred compounds of this type in acid form aredihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelator for use herein is ethylenediaminedisuccinate (“EDDS”), especially the [S,S] isomer as described in U.S.Pat. No. 4,704,233, Nov. 3, 1987, to Hartman and Perkins.

The compositions herein may also contain water-soluble methyl glycinediacetic acid (MGDA) salts (or acid form) as a chelant or cobuilderuseful with, for example, insoluble builders such as zeolites, layeredsilicates and the like. If utilized, these chelating agents willgenerally comprise from about 0.1% to about 15% by weight of the fabriccare compositions herein. More preferably, if utilized, the chelatingagents will comprise from about 0.1% to about 3.0% by weight of suchcompositions.

Suds Suppressor

Another optional ingredient is a suds suppressor, exemplified bysilicones, and silica-silicone mixtures. Silicones can be generallyrepresented by alkylated polysiloxane materials while silica is normallyused in finely divided forms exemplified by silica aerogels and xerogelsand hydrophobic silicas of various types. These materials can beincorporated as particulates in which the suds suppressor isadvantageously releasably incorporated in a water-soluble orwater-dispersible, substantially non-surface-active detergentimpermeable carrier. Alternatively the suds suppressor can be dissolvedor dispersed in a liquid carrier and applied by spraying on to one ormore of the other components.

A preferred silicone suds controlling agent is disclosed in Bartollotaet al. U.S. Pat. No. 3,933,672. Other particularly useful sudssuppressors are the self-emulsifying silicone suds suppressors,described in German Patent Application DTOS 2 646 126 published Apr. 28,1977. An example of such a compound is DC-544, commercially availablefrom Dow Coming, which is a siloxane-glycol copolymer. Especiallypreferred suds controlling agent are the suds suppressor systemcomprising a mixture of silicone oils and 2-alkyl-alcanols. Suitable2-alkyl-alkanols are 2-butyl-octanol which are commercially availableunder the trade name Isofol 12 R.

Such suds suppressor system are described in Copending European Patentapplication N 92870174.7 filed 10 Nov. 1992.

Especially preferred silicone suds controlling agents are described inCopending European Patent application No. 92201649.8. Said compositionscan comprise a silicone/silica mixture in combination with fumednonporous silica such as Aerosil^(R).

The suds suppressors described above are normally employed at levels offrom 0.001% to 2% by weight of the composition, preferably from 0.01% to1% by weight.

Method

In another aspect of the invention, there is provided a method forproviding fabric care to fabrics upon domestic treatment which comprisesthe step of contacting the fabrics with an aqueous medium comprising acomposition as defined hereinbefore. Preferably, said aqueous medium isat a temperature between 2 to 40° C., more preferably between 5 to 25°C.

In a further aspect of the invention, the composition of the inventionmay be applied on a substrate, such as a dryer-sheet. Accordingly, thereis also provided a method for providing fabric care on treated fabricsupon domestic treatment which comprises the step of contacting thefabrics with a composition as defined hereinbefore, wherein saidcomposition is applied on a substrate, preferably a dryer-sheet.Preferably, where the composition of the invention is applied on adryer-sheet, the compositions are used in tumble-drying processes.

The compositions of the invention are suitable for use in any steps ofthe domestic treatment, that is as a pretreatment composition, as a washadditive as a composition suitable for use in the rinse-cycle of thelaundry cycle or applied on a dryer-sheet. Obviously, for the purpose ofthe invention, multiple applications can be made such as treating thefabric with a pre-treatment composition of the invention and alsothereafter with a composition of the invention suitable for use in therinse cycle and/or suitable for use as a dryer-sheet. The compositionsof the invention may also be in a spray, foam, or aerosol form which forexample can be suitable for use while ironing, or applied on thesurfaces of the tumble dryer.

When formulated as “softening through the wash” compositions, theprocess described herein comprises contacting fabrics with a launderingsolution in the usual manner and exemplified hereunder. A conventionallaundry method comprises treating soiled fabric with an aqueous liquidhaving dissolved or dispensed therein an effective amount of the laundrydetergent and/or fabric care composition. The process of the inventionis conveniently carried out in the course of the cleaning process. Themethod of cleaning is preferably carried out at 5° C. to 95° C.,especially between 10° C. and 60° C. The pH of the treatment solution ispreferably from 7 to 12.

EXAMPLE

The following examples are meant to exemplify compositions of thepresent invention, but are not necessarily meant to limit or otherwisedefine the scope of the invention.

In the fabric care compositions, the enzymes levels are expressed bypure enzyme by weight of the total composition and unless otherwisespecified, the detergent ingredients are expressed by weight of thetotal compositions. The abbreviated component identifications thereinhave the following meanings:

LAS: Sodium linear C₁₁₋₁₃ alkyl benzene sulphonate. CxyAS: SodiumC_(1x)-C_(1y) alkyl sulfate. CxyEz: C_(1x)-C_(1y) predominantly linearprimary alcohol condensed with an average of z moles of ethylene oxide.DEQA: Di-(tallow-oxy-ethyl)dimethyl ammonium chloride. DEQA (2):Di-(soft-tallowyloxyethyl)hydroxyethyl methyl ammonium methylsulfate.DTDMAMS: Ditalllow dimethyl ammonium methylsulfate. SDASA: 1:2 ratio ofstearyldimethyl amine:triple-pressed stearic acid. Zeolite A: HydratedSodium Aluminosilicate of formula Na₁₂(AlO₂SiO₂)₁₂.27H₂O having aprimary particle size in the range from 0.1 to 10 micrometers (Weightexpressed on an anhydrous basis). Na-SKS-6: Crystalline layered silicateof formula δ-Na₂Si₂O₅. Citrate: Tri-sodium citrate dihydrate of activity86.4% with a particie size distribution between 425 and 850 micrometers.Carbonate: Anhydrous sodium carbonate with a particle size between 200and 900 micrometers. MA/AA: Random copolymer of 4:1 acrylate/maleate,average molecular weight about 70,000-80,000. PB1: Anhydrous sodiumperborate monohydrate of nominal formula NaBO₂.H₂O₂. Percarbonate:Anhydrous sodium percarbonate of nominal formula 2Na₂CO₃.3H₂O₂. TAED:Tetraacetylethylenediamine. DETPMP: Diethyltriaminepenta(methylene)phosphonate, marketed by Monsanto under the Trade nameDequest 2060. Protease: Proteolytic enzyme sold under the tradenameSavinase, Alcalase, Durazym by Novo Nordisk NS, Maxacal, Maxapem sold byGist-Brocades and proteases described in patents WO91/06637 and/orWO95/10591. Amylase: Amylolytic enzyme sold under the tradename PurafactOx Am ® described in WO94/18314, WO96/05295 sold by Genencor;Termamyl ®, Fungamyl ® and Duramyl ®, all available from Novo NordiskA/S and those described in WO95/26397. Lipase: Lipolytic enzyme soldunder the tradename Lipolase, Lipolase Ultra by Novo Nordisk A/S andLipomax by Gist-Brocades. Cellulase: Cellulytic enzyme sold under thetradename Carezyme, Celluzyme and/or Endolase by Novo Nordisk A/S. CBD1:Double CBD comprising the N-terminal CBD of Trichoderma reesei CBHIIlinked to the C-terminal CBD of CBHI via a linking region of 24 aminoacid (M. Linder et al - The Journal of Biological Chemistry, Vol. 271.No. 35, issue of August, pp 21268-21272, 1996) CBD2: CBD Cellulozomefrom Clostridium cellulovorans, which is sold under the tradenameCellulose Binding Domain by Sigma, linked to a C18 alkyl quaternary weatprotein derivative sold under the tradename Coltide HQS by CrodaColloids Ltd. CMC: Sodium carboxymethyl cellulose. Silicone antifoam:Polydimethylsiloxane foam controller with siloxane- oxyalkylenecopolymer as dispersing agent with a ratio of said foam controller tosaid dispersing agent of 10:1 to 100:1. Suds Suppressor: 12%Silicone/silica, 18% stearyl alcohol, 70% starch in granular form.HMWPEO: High molecular weight polyethylene oxide.

Example 1

The following granular fabric detergent compositions which provide“softening through the wash” capability were prepared according to thepresent invention:

I II C45AS — 10.0 LAS 7.6 — C68AS 1.3 — C25E7 4.0 — C25E3 — 5.0Coco-alkyl-dimethyl hydroxyethyl ammonium 1.4 1.0 chloride Citrate 5.03.0 Na-SKS-6 — 11.0 Zeolite A 15.0 15.0 MA/AA 4.0 4.0 DETPMP 0.4 0.4 PB115.0 — Percarbonate — 15.0 TAED 5.0 5.0 Smectite clay 10.0 10.0 HMWPEO —0.1 Protease 0.02 0.01 Lipase 0.002 0.01 Amylase 0.03 0.005 Cellulase0.001 0.0005 CBD1 — 2.0 CBD2 0.2 — Silicate 3.0 5.0 Carbonate 10.0 10.0Suds suppressor 1.0 4.0 CMC 0.2 0.1 Water/minors Up to 100%

Example 2

The following rinse added fabric softener compositions were preparedaccording to the present invention:

I II III CBD1 — 2.0 0.5 CBD2 0.2 — 0.05 DEQA (2) 20.0 20.0 20.0Cellulase 0.001 0.001 0.001 HCL 0.03 0.03 0.03 Antifoam agent 0.01 0.010.01 Blue dye 25 ppm 25 ppm 25 ppm CaCl₂ 0.20 0.20 0.20 Perfume 0.900.90 0.90 Miscellaneous and water Up to 100%

Example 3

The following fabric softener and dryer added fabric conditionercompositions were prepared according to the present invention:

I II III IV V DEQA 2.6 19.0 — — — DEQA (2) — — — — 51.8 DTMAMS — — —26.0 — SDASA — — 70.0 42.0 40.2 Stearic acid of IV = 0 0.3 — — — —Neodol 45-13 — — 13.0 — — Hydrochloride acid 0.02 0.02 — — — Ethanol — —1.0 — — Cellulase 0.0001 0.001 0.0005 0.005 0.0003 CBD1 — 1.0 1.0 — 5.0CBD2 0.2 — — 0.2 — Perfume 1.0 1.0 0.75 1.0 1.5 Glycoperse S-20 — — — —15.4 Glycerol monostearate — — — 26.0 — Digeranyl Succinate — — 0.38 — —Silicone antifoam 0.01 0.01 — — — Electrolyte — 0.1 — — — Clay — — — 3.0— Dye 10 ppm 25 ppm 0.01 — — Water and minors 100% 100% — — —

Example 4

The following pre- or post treatment compositions were prepared inaccord with the present invention:

I II III CBD1 2.0 1.0 — CBD2 — — 0.4 DEQA (2) — 20.0 20.0 Cellulase0.002 0.001 0.001 HCL — 0.03 0.03 Antifoam agent — 0.01 0.01 Blue dye 25ppm 25 ppm 25 ppm CaCl₂ — 0.20 0.20 Perfume 0.90 0.90 0.90 Water/minorsUp to 100%

1. A fabric softening protein hybrid comprising an amino acid sequencecomprising a cellulose binding domain linked to a fabric softeningprotein; wherein said fabric softening protein is linked to said aminoacid sequence comprising a cellulose binding domain, via a non-aminoacid linking region; wherein the cellulose binding domain is selectedfrom the group consisting of CBD Cellulozome from Clostridiumcellulovorans, CBD E3 from Thermonospora fusca, CBD-dimer fromClostridium stecorarium XynA, CBD from Bacillus agaradherens, andcombinations thereof; further wherein said non-amino linking region is apolymer selected from the group consisting of polyethylene glycolderivatives, nucleophilic polyethylene glycol derivatives, carboxylpolyethylene glycol derivatives, electrophilically activatedpolyethylene glycol derivatives, sulfhydryl-selective polyethyleneglycol derivatives, heterofunctional polyethylene glycol derivatives,biotin polyethylene glycol derivatives, vinyl polyethylene glycolderivatives, silane polyethylene glycol derivatives, phospholipidpolyethylene glycol derivatives, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, N-ethyl-5-phenylisoaxolium-3-sulphonate,1-cyclohexyl-3(2-morpholinoethyl) carbodide metho-p-toluene sulphonate,N-ethoxycarbonyl-2-ethoxy 1,2, dihydroquinoline, glutaraldehyde andmixtures thereof; and further wherein said fabric softening protein isselected from the group consisting of: hydrolases, lyases,oxidoreductases, ligases, transferases, isomerases, cellulases,xylanases, mannanases, arabinofuranosidases, acetylesterases,chitinases, polyamino acid resin solutions, C₁₈ alkyl quaternary wheatprotein derivatives and combinations thereof.
 2. A fabric carecomposition comprising the fabric softening protein hybrid according toclaim
 1. 3. A fabric softening protein hybrid according to claim 1wherein the amino acid sequence comprising a cellulose binding domain isselected from CBD Cellulozome from Clostridium cellulovorans.
 4. Afabric care composition according to claim 2 further comprising anotherfabric care ingredient.
 5. A fabric care composition according to claim2 further comprising a fabric care ingredient wherein said fabric careingredient is selected from the group consisting of a cationicsurfactant comprising two long alkyl chain lengths, a clay, atransferase and/or mixtures thereof.
 6. A method comprising the step ofcontacting a fabric with a fabric care composition according to claim 2to provide fabric softness, anti-wrinkle properties, anti-bobblingproperties, anti-shrinkage properties, static control, colour appearanceand fabric anti-wear properties and to provide, refurbish or restoretensile strength.